Preparation of preparing substituted indanones

ABSTRACT

A process for the preparation of indanones of the formula II from indanones of the formula I or of indanones of the formula IIa from indanones of the formula Ia 
                 
 
comprises reacting an indanone of the formula I or Ia with a coupling component.

This application is a divisional of Ser. No. 09/380,396 Sep. 01, 1999now U.S. Pat. No. 6,492,539, which is a 371 of PCT/EP98/01232 Mar. 05,1998.

The present invention relates to a simple and economically interestingprocess for preparing substituted indanones.

Substituted indanones are important intermediates for preparing activecompounds in the fields of pharmacy and crop protection (cf. S. J.deSolms et al., J. Med. Chem., 1978, 21, 437) and for preparingmetallocene complexes (cf. Chemie in unserer Zeit, 1994, 28, 204, 205).In particular, substituted indanones can be used to prepare bridgedchiral metallocenes which are of great importance as highly activecatalysts in olefin polymerization (cf. EP-A 129 368). The catalystproperties can be influenced in a targeted manner by variation of theligand system, eg. by substitution. This makes it possible to achievethe desired degree of change in the polymer yield, the tacticity or themelting point of the polymers (New J. Chem., 1990, 14, 499; Organomet.,1990, 9, 3098; Angew. Chem., 1990, 102, 339; EP-A 316 155; EP-A 351392). Bridged zirconocenes containing, as π ligands, substituted indenylradicals which bear the bridge in position 1, preferably a hydrocarbonradical in position 2 and a hydrocarbon radical, preferably an arylradical, in position 4 have been found to be particularly active andstereoselective catalyst systems (EP 0 576 970 A1; EP 0 629 632 A2). Theligand systems used for these highly active metallocenes are preparedfrom the corresponding indenes which are in turn obtained from indanoneswhich are substituted in the appropriate positions (EP 0 576 970 A1; EP0 629 632 A2). These indanones are synthesized from commerciallyavailable precursors or precursors known in the literature, for exampleas follows:

The 2-methyl-4-phenylindanone is converted into the correspondingindene, for example by reduction of the ketone function to the alcoholand subsequent dehydration.EP 0 629 632 A2:

The three synthetic routes shown by way of example go through 2-,4-substituted indanones which have in each case been obtained byFriedel-Crafts cyclization of the corresponding 3-arylpropionic acids.The syntheses are multistage processes in which relatively expensivestarting compounds are used. Furthermore, in the syntheses disclosed inEP 0 629 632, the introduction of a protective group cannot be avoided.The processes shown are thus very costly routes.

It is therefore an object of the present invention to find a simple,flexible, inexpensive process for preparing substituted indanones whichare important intermediates for preparing active compounds andmetallocene complexes.

We have now surprisingly found that substituted indanones which containa leaving group can be used to prepare, in a simple manner, otherindanones which can be used, inter alia, for preparing active compoundsand metallocene complexes.

The present invention accordingly provides a process for the preparationof indanones of the formula II from indanones of the formula I or ofindanones of the formula IIa from indanones of the formula Ia

which comprises reacting an indanone of the formula I or Ia with acoupling component, where, in the formulae I, Ia, II and IIa,

R¹ is a C₁-C₄₀-group such as a C₁-C₄₀-hydrocarbon group which is boundvia a carbon atom and may bear one or more identical or differentheteroatom-containing radicals as substituents, eg. a linear, branchedor cyclic C₁-C₂₀-alkyl group which may bear one or more identical ordifferent halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents, a C₆-C₂₂-aryl group which may bear one or more identicalor different halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents, a C₇-C₂₀-alkylaryl group or a C₇-C₂₀-arylalkyl group,where the alkyl part may bear one or more identical or differenthalogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituentsand the aryl part may bear one or more identical or different halogen,OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, aC₂-C₁₀-alkenyl group which may bear one or more identical or differenthalogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, aC₂-C₂₀-alkynyl group which may bear one or more identical or differenthalogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, aC₈-C₁₂-arylalkenyl group, where the alkenyl part may bear one or moreidentical or different halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents and the aryl part may bear one or more identicalor different halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents,

or R¹ is an OR², SR², NR² ₂, PR² ₂, SiR² ₃ or OSiR² ₃ group, where R²are identical or different and are each a C₁-C₂₀-hydrocarbon group suchas a C₁-C₁₀-alkyl group or C₆-C₁₄-aryl group which may each bear one ormore identical or different halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃or —OSiR² ₃ substituents or two radicals R² may be joined to form a ringsystem,

or R¹ is a C₁-C₂₀-heterocyclic group which is bound via a carbon atomand may in turn bear C₁-C₂₀-radicals or heteroatoms as substituents,

x is a leaving group such as a diazonium group, a halogen atom or aC₁-C₄₀-, preferably C₁-C₁₀-group which is bound via a heteroatom such asan atom of Group 13, 14, 15 or 16 of the Periodic Table of the Elements,eg. boron, silicon, tin, oxygen or sulfur, for exampleC₁-C₄₀-alkylsulfonate, C₁-C₄₀-haloalkylsulfonate, C₆-C₄₀-arylsulfonate,C₆-C₄₀-haloarylsulfonate, C₇-C₄₀-arylalkylsulfonate,C₇-C₄₀-haloarylalkylsulfonate, C₁-C₄₀-alkylcarboxylate,C₁-C₄₀-haloalkylcarboxylate, C₆-C₄₀-arylcarboxylate,C₆-C₄₀-haloarylcarboxylate, C₇-C₄₀-arylalkylcarboxylate,C₇-C₄₀-haloarylalkylcarboxylate, formate, C₁-C₄₀-alkyl carbonate,C₁-C₄₀-haloalkyl carbonate, C₆-C₄₀-aryl carbonate, C₆-C₄₀-haloarylcarbonate, C₇-C₄₀-arylalkyl carbonate, C₇-C₄₀-haloarylalkyl carbonate,C₁-C₄₀-alkyl phosphonate, C₁-C₄₀-haloalkyl phosphonate, C₆-C₄₀-arylphosphonate, C₆-C₄₀-haloaryl phosphonate, C₇-C₄₀-arylalkyl phosphonateor C₇-C₄₀-haloarylalkyl phosphonate,

R³ is a C₁-C₄₀-hydrocarbon group which is bound via a carbon atom andmay bear one or more identical or different heteroatom-containingradicals as substituents, for example a linear, branched or cyclicC₁-C₂₀-alkyl group which may bear one or more identical or differenthalogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents,a C₆-C₂₂-aryl group which may bear one or more identical or differenthalogen, OR², SR², NR² ₂—, NH₂, —N₂H₃, NO₂, CN, CO₂R², CHO, COR², PR²₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₇-C₁₅-alkylaryl group orC₇-C₁₅-arylalkyl group, where the alkyl part may bear one or moreidentical or different halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents and the aryl part may bear one or more identicalor different halogen, OR², SR²NR² ₂—, NH₂, —N₂H₃, NO₂, CN, CO₂R², CHO,PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₂-C₁₀-alkenyl group whichmay bear one or more identical or different halogen, OR, OR², CO₂R²,COR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, aC₂-C₁₀-alkynyl group which may bear one or more identical or differenthalogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents,a C₈-C₁₂-arylalkenyl group which may bear one or more identical ordifferent halogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents,

or R³ is a halogen atom or a PR² ₂, B(OR²)₂, SiR² ₃ or SnR² ₃ group,where R² are identical or different and are each a C₁-C₂₀-hydrocarbongroup, eg. a C₁-C₁₀-alkyl group or C₆-C₁₄-aryl group which may each bearone or more identical or different halogen, OH, OR², SR²NR² ₂—, PR² ₂—,—SiR² ₃ or —OSiR² ₃ substituents, or two radicals R² may be joined toform a ring system,

or R³ is a C₁-C₂₀-heterocyclic group which is bound via a carbon atomand may in turn bear C₁-C₂₀-radicals or heteroatoms as substituents,

Y¹, Y² and Y³ are identical or different and are each a hydrogen atom orare as defined for X or R³, and

Y⁴, Y⁵ and Y⁶ are identical or different and are each a hydrogen atom orare as defined for R³.

In the process of the present invention, the indanones of the formula Ior Ia are converted directly into the indanones of the formula II or IIain one reaction step by reaction with the coupling component. In thisreaction, no use is made of protective groups for the carbonyl functionof the indanone of the formula I or Ia.

For the purposes of this application, the term “heteroatom” refers toany atom of the Periodic Table of the Elements with the exception ofcarbon and hydrogen. A heteroatom is preferably an atom of Group 14, 15or 16 of the Periodic Table of the Elements with the exception ofcarbon. The term “heterocyclic group” refers to a heteroatom-containingcyclic group.

In the process of the present invention, particular preference is givento using indanones of the formula I or Ia in which

X is chlorine, bromine, iodine, triflate, nonaflate, mesylate,ethylsulfonate, benzenesulfonate, tosylate,triisopropylbenzenesulfonate, formate, acetate, trifluoroacetate,nitrobenzoate, halogenated arylcarboxylates, in particular fluorinatedbenzoate, methyl carbonate, ethyl carbonate, benzyl carbonate,tert-butyl carbonate, dimethyl phosphonate, diethyl phosphonate,diphenyl phosphonate or diazonium,

R¹ is a linear, branched or cyclic C₁-C₈-alkyl group which may bear oneor more identical or different fluorine, chlorine, OR², PR² ₂—, NR² ₂—,—SiR² ₃ or —OSiR² ₃ substituents, a C₆-C₁₀-aryl group which may bear oneor more identical or different fluorine, chlorine, OR², SR², NR² ₂—, PR²₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₇-C₁₂-alkylaryl or arylalkylgroup, where the alkyl part may bear one or more identical or differentfluorine, chlorine, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents and the aryl part may bear one or more identical ordifferent fluorine, chlorine, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents, a C₂-C₈-alkenyl group or a C₂-C₈-alkynyl groupwhich may each bear one or more identical or different fluorine,chlorine, OR² or NR² ₂ substituents, a C₈-C₁₂-arylalkenyl group whichmay bear one or more identical or different fluorine, chlorine, OR² orNR² ₂ substituents, or R¹ is an OR², PR² ₂, NR² ₂, —SiR² ₃ or —OSiR² ₃group, where R² are identical or different and are each a C₁-C₄-alkylgroup or C₆-C₁₀-aryl group, where the alkyl group may bear one or moreidentical or different fluorine, chlorine, OR², SR², NR² ₂—, PR² ₂—,—SiR² ₃ or —OSiR² ₃ substituents and the aryl group may bear one or moreidentical or different fluorine, chlorine, OR², SR², NR² ₂—, PR² ₂—,—SiR² ₃ or —OSiR² ₃ substituents, or R¹ is a C₁-C₂₀-heterocyclic group,with preferred heteroatoms being oxygen, nitrogen, sulfur, phosphorusand silicon, which may in turn bear C₁-C₂₀-radicals or heteroatoms assubstituents,

R³ is a C₁-C₂₀-group such as a linear, branched or cyclic C₁-C₁₀-alkylgroup which may bear one or more identical or different fluorine, OR²,NR² ₂— or —OSiR² ₃ substituents, a C₁-C₁₀-aryl group which may bearfluorine, chlorine, OR², SR², NR² ₂, NH₂, NO₂, CN, COR₂ or CO₂R₂substituents, a C₇-C₁₅-alkylaryl group or C₇-C₁₅-arylalkyl group, wherethe alkyl part may bear one or more identical or different fluorine,OR², NR² ₂— or OSiR² ₃ substituents, and the aryl part may bearfluorine, chlorine, OR², SR², NR² ₂—, NH₂, NO₂, CN, COR² or CO²R²substituents, a C₂-C₁₀-alkenyl group which may bear one or moreidentical or different fluorine, OR², CO²R², COR², NR² ₂— or OSiR² ₃substituents, a C₂-C₁₀-alkynyl group which may bear one or moreidentical or different fluorine, OR², NR² ₂— or OSiR² ₃ substituents, aC₈-C₁₂-arylalkenyl group, a PR² ₂, B(OR²)₂ or SnR² ₃ group, where R² areidentical or different and are each a C₁-C₄-alkyl group or C₆-arylgroup, where the alkyl group may bear one or more identical or differentfluorine, chlorine, OR² or NR² ₂ substituents and the aryl group maybear fluorine, chlorine, OR² or NR² ₂ substituents and, in addition, tworadicals R² may be joined to one another to form a ring system, aC₁-C₁₄-heterocyclic group, where preferred heteroatoms are oxygen,nitrogen or sulfur and the group may in turn bear C₁-C₆-radicals orheteroatoms as substituents,

Y¹, Y² and Y³ are identical or different and are each a hydrogen atom orare as defined for R³ or X and at least one of the radicals Y¹, Y² andY³, preferably Y³, is a hydrogen atom,

Y⁴, Y⁵ and Y⁶ are identical or different and are each a hydrogen atom orare as defined for R³ and at least one of the radicals Y⁴, Y⁵ and Y⁶,preferably Y⁶, is a hydrogen atom.

Very particular preference is given to indanones of the formula I or Iain which X is chlorine, bromine, iodine, triflate, nonaflate, mesylate,tosylate or diazonium,

R¹ is a linear, branched or cyclic C₁-C₈-alkyl group which may bear oneor more identical or different fluorine, chlorine, OR² or NR² ₂substituents, a phenyl group which may bear one or more identical ordifferent fluorine, chlorine, OR² or NR² ₂ substituents, aC₇-C₁₂-alkylaryl or arylalkyl group, where the alkyl part may bear oneor more identical or different fluorine, chlorine, OR² or NR² ₂substituents and the aryl part may bear one or more identical ordifferent fluorine, chlorine, OR² or NR² ₂ substituents, a C₂-C₈-alkenylgroup or a C₂-C₈-alkynyl group which may each bear one or more identicalor different fluorine, chlorine, OR² or NR² ₂ substituents, aC₈-C₁₂-arylalkenyl group which may bear one or more identical ordifferent fluorine, chlorine, OR² or NR² ₂ substituents, or R¹ is anOR², SiR² ₃ or —OSiR² ₃ group, where R² are identical or different andare each a C₁-C₄-alkyl group or phenyl group, where the alkyl group maybear one or more identical or different fluorine, chlorine, OR² or NR² ₂substituents and the aryl group may bear one or more identical ordifferent fluorine, chlorine, OR² or NR² ₂ substituents, or R¹ is aC₁-C₁₆-heterocyclic group, where preferred heteroatoms are oxygen,nitrogen, sulfur and silicon and the group may in turn bearC₁-C₁₀-radicals or heteroatoms as substituents,

Y¹, Y² or Y³ are identical or different and are each a hydrogen atom,chlorine, bromine, iodine, triflate, nanoflate, mesylate, tosylate ordiazonium, or Y¹, Y² or Y³ are each a linear, branched or cyclicC₁-C₈-alkyl group which may bear one or more identical or differenthalogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, aC₆-C₁₄-aryl group which may bear one or more identical or differenthalogen, OR², SR²NR² ₂—, NH₂, —N₂H₃, NO₂, CN, CO₂R², CHO, COR², PR² ₂—,—SiR² ₃ or —OSiR² ₃ substituents, a C₇-C₁₅-alkylaryl group orC₇-C₁₅-arylalkyl group, where the alkyl part may bear one or moreidentical or different halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents and the aryl part may bear one or more identicalor different halogen, OR², SR²NR² ₂—, NH₂, —N₂H₃, NO₂, CN, CO₂R², CHO,PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₂-C₁₀-alkenyl group whichmay bear one or more identical or different halogen, OH, OR², SR², NR²₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₂-C₈-alkynyl groupwhich may bear one or more identical or different halogen, OH, OR², SR²,NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₈-C₁₂-arylalkenylgroup which may bear one or more identical or different halogen, OH,OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents,

or Y¹, Y² or Y³ are each a halogen atom or an NR² ₂, PR² ₂, B(OR²)₂,SiR² ₃ or SnR² ₃ group, where R² are identical or different and are eacha C₁-C₂₀-hydrocarbon group, eg. a C₁-C₁₀-alkyl group or C₆-C₁₄-arylgroup which may each bear one or more identical or different halogen,OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, or tworadicals R² may be joined to form a ring system, or Y¹, Y² or Y³ areeach a C₁-C₂₀-heterocyclic group which is bound via a carbon atom andmay in turn bear C₁-C₂₀-radicals or heteroatoms as substituents, and atleast two of the radicals Y¹, Y² and Y³ are each a hydrogen atom,preferably Y¹ and Y³.

R³ is a C₁-C₁₄-group such as a linear, branched or cyclic C₁-C₈-alkylgroup which may bear one or more identical or different fluorine,OR^(2a), NR^(2a) ₂— or OSiR^(2a) ₃ substituents, a C₆-C₁₄-aryl groupwhich may bear fluorine, chlorine, R², OR^(2a) or NR^(2a) ₂substituents, a C₇-C₁₀-alkylaryl group or C₇-C₁₀-arylalkyl group, wherethe alkyl part may bear one or more identical or different fluorine,OR^(2a), NR^(2a) ₂— or OSiR^(2a) ₃ substituents and the aryl part maybear one or more identical or different fluorine, chlorine, OR^(2a) orNR^(2a) ₂ substituents, a C₂-C₈-alkenyl group which may bear one or moreidentical or different fluorine, OR^(2a), CO²R^(2a) or NR^(2a) ₂substituents, a C₂-C₈-alkynyl group which may bear one or more identicalor different fluorine, OR^(2a) or NR^(2a) ₂ substituents, aC₈-C₁₂-arylalkenyl group, a PR^(2a) ₂, B(OR^(2a))₂ or SnR^(2a) ₃ group,where R^(2a) are identical or different and are each a linear orbranched C₁-C₄-alkyl group which may bear one or more fluorinesubstituents, or a phenyl group which may bear one or more identical ordifferent fluorine or OR^(2a) substituents, and, in addition, tworadicals R^(2a) may be joined to one another to form a ring system, aC₁-C₁₄-heterocyclic group, where preferred heteroatoms are oxygen,nitrogen or sulfur and the group may in turn bear C₁-C₄-radicals orheteroatoms as substituents, and Y⁴, Y⁵ and Y⁶ are identical ordifferent and are each a hydrogen atom or R³ and at least two of theradicals Y⁴, Y⁵ and Y⁶ are hydrogen, preferably Y⁴ and Y⁶.

Illustrative examples of indanones of the formula I, which do not,however, restrict the scope of the invention, are:

2-methyl-7-chloro-1-indanone

2-methyl-7-bromo-1-indanone

2-methyl-7-iodo-1-indanone

2-methyl-7-trifluoroacetoxy-1-indanone

2-methyl-7-trifluoromethanesulfonoxy-1-indanone

2-methyl-7-methanesulfonoxy-1-indanone

2-methyl-7-ethanesulfonoxy-1-indanone

2-methyl-7-(p-toluenesulfonoxy)-1-indanone

2-methyl-7-benzenesulfonoxy-1-indanone

2-methyl-7-(2,4,6-triisopropylbenzenesulfonoxy)-1-indanone

2-methyl-7-pentafluorobenzenesulfonoxy-1-indanone

2-methyl-7-nonafluorobutanesulfonoxy-1-indanone

2-methyl-7-acetoxy-1-indanone

2-methyl-7-formyloxy-1-indanone

2-methyl-7-pentafluorobenzoyloxy-1-indanone

2-methyl-7-(p-nitrobenzoyloxy)-1-indanone

2-methyl-7-methoxycarbonyloxy-1-indanone

2-methyl-7-tert-butyloxycarbonyloxy-1-indanone

2-methyl-7-ethoxycarbonyloxy-1-indanone

2-methyl-7-benzyloxycarbonyloxy-1-indanone

2-methyl-7-dimethylphosphonoxy-1-indanone

2-methyl-7-diethylphosphonoxy-1-indanone

2-methyl-7-diphenylphosphonoxy-1-indanone

2-methyl-7-diazonium-1-indanone chloride

2-methyl-7-diazonium-1-indanone tetrafluoroborate

2-methyl-7-diazonium-1-indanone sulfate

2-methyl-4-vinyl-7-bromo-1-indanone

2-methyl-5-butyl-7-bromo-1-indanone

2-methyl-5-fluoro-7-bromo-1-indanone

2-methyl-4-isopropyl-7-bromo-1-indanone

2-methyl-5,7-dibromo-1-indanone

2-methyl-5,7-dichloro-1-indanone

2-methyl-6,7-dichloro-1-indanone

2-methyl-5-chloro-7-bromo-1-indanone

2-methyl-4-phenyl-7-diazonium-1-indanone chloride

2-methyl-4-cyclohexyl-7-diazonium-1-indanone tetrafluoroborate

2,5-dimethyl-7-chloro-1-indanone

2,4-dimethyl-7-bromo-1-indanone

2,6-dimethyl-7-chloro-1-indanone

2-methyl-5-butyl-7-chloro-1-indanone

2-methyl-5-isopropyl-7-trifluoromethanesulfonoxy-1-indanone

2-methyl-5-tert-butyl-7-methanesulfonoxy-1-indanone

2-methyl-5-phenyl-7-bromo-1-indanone

2-methyl-5-(3,5-dimethoxyphenyl)-7-iodo-1-indanone

2-methyl-5-benzyl-7-chloro-1-indanone

2-methyl-5-methoxy-7-chloro-1-indanone

2-methyl-5-phenoxy-7-chloro-1-indanone

2-methyl-6-methoxy-7-chloro-1-indanone

2-methyl-6-isopropoxy-7-bromo-1-indanone

2-methyl-6-trimethylsilyloxy-7-bromo-1-indanone

2-methyl-5-vinyl-7-(p-toluenesulfonoxy)-1-indanone

2-methyl-6-bromo-7-trifluoroacetoxy-1-indanone

2-methyl-6-phenyl-7-bromo-1-indanone

2-methyl-4-methoxy-7-chloro-1-indanone

2-methyl-4-diisopropylamino-7-chloro-1-indanone

2-trifluoromethyl-7-chloro-1-indanone

2-trifluoromethyl-7-bromo-1-indanone

2-trifluoromethyl-4-methyl-7-chloro-1-indanone

2-trifluoromethyl-5-isobutyl-7-trifluoromethanesulfonoxy-1-indanone

2-ethyl-7-chloro-1-indanone

2-ethyl-7-bromo-1-indanone

2-ethyl-7-diazonium-1-indanone tetrafluoroborate

2-ethyl-7-methanesulfonoxy-1-indanone

2-ethyl-4-trimethylsilyloxy-7-trifluoromethanesulfonoxy-1-indanone

2-ethyl-5-methyl-7-bromo-1-indanone

2-ethyl-4-benzyl-7-bromo-1-indanone

2-ethyl-7-diazonium-1-indanone tetrafluoroborate

2-n-propyl-7-chloro-1-indanone

2-n-propyl-7-bromo-1-indanone

2-n-propyl-5,7-dichloro-1-indanone

2-n-propyl-7-trifluoromethanesulfonoxy-1-indanone

2,6-diethyl-7-diazonium-1-indanone chloride

2-butyl-7-chloro-1-indanone

2-butyl-5-fluoro-7-chloro-1-indanone

2-butyl-5,7-dichloro-1-indanone

2-isopropyl-7-chloro-1-indanone

2-isopropyl-7-bromo-1-indanone

2-isopropyl-7-iodo-1-indanone

2-isopropyl-5-diphenylphosphino-7-nonafluorobutanesulfonoxy-1-indanone

2-phenyl-4-dimethylamino-7-bromo-1-indanone

2-phenyl-7-chloro-1-indanone

2-(2-pyridyl)-7-bromo-1-indanone

2-(2-furyl)-7-iodo-1-indanone

2-cyclohexyl-7-chloro-1-indanone

2-cyclohexyl-7-bromo-1-indanone

2-cyclohexyl-7-trifluoromethanesulfonoxy-1-indanone

2-isobutyl-7-chloro-1-indanone

2-isobutyl-7-bromo-1-indanone

2-tert-butyl-7-chloro-1-indanone

2-tert-butyl-7-iodo-1-indanone

2-benzyl-7-chloro-1-indanone

2-allyl-7-chloro-1-indanone

2-vinyl-7-trifluoromethanesulfonoxy-1-indanone

2-(2-trimethylsilylethyn-1-yl)-6-benzyl-7-chloroindanone

2-(hex-1-ynyl)-7-trifluoromethanesulfonoxy-1-indanone

2-trimethylsilyl-7-bromo-1-indanone

2-trimethylsilyloxy-7-bromo-1-indanone

2-dimethylamino-7-trifluoromethanesulfonoxy-1-indanone

2-N-pyrrolidino-7-chloro-1-indanone

2-diphenylphosphino-5-isopropyl-7-bromo-1-indanone

2-methoxy-6-allyl-7-chloro-1-indanone

2,6-dimethoxy-7-bromo-1-indanone

2-phenoxy-5-dimethylamino-7-trifluoromethanesulfonoxy-1-indanone

2-(2-methoxyethyl)-7-chloro-1-indanone

2-(3-chloropropyl)-7-chloro-1-indanone

2,4,5,6-tetramethyl-7-chloro-1-indanone

2-methyl-4-phenyl-5-methoxy-7-bromo-1-indanone

2-butyl-5-benzyl-6-bromo-7-trifluoromethanesulfonoxy-1-indanone

2-trimethylsilyloxy-4-methoxy-5-allyl-7-diazonium-1-indanonetetrafluoroborate

2-N-piperidino-4-fluoro-5,7-dibromo-1-indanone

2-isopropyl-4-cyclohexyl-5-methyl-7-trimethylstannyl-1-indanone

2,5-dimethoxy-4-bromo-6-trifluoromethyl-7-iodo-1-indanone

2-ethyl-4-dimethylamino-5-trimethylsilyl-7-chloroindanone

2-trifluoroethoxy-4-thiomethoxy-6-butyl-7-bromo-1-indanone

2-triethylsilyl-5,6-difluoro-7-methanesulfonoxy-1-indanone

2,5-diphenyl-7-bromo-1-indanone

Illustrative examples of indanones of the formula Ia, which, however, donot restrict the scope of the invention, are:

2-methyl-4-chloro-1-indanone

2-methyl-4-bromo-1-indanone

2-methyl-4-iodo-1-indanone

2-methyl-4-trifluoroacetoxy-1-indanone

2-methyl-4-trifluoromethanesulfonoxy-1-indanone

2-methyl-4-methanesulfonoxy-1-indanone

2-methyl-4-ethanesulfonoxy-1-indanone

2-methyl-4-(p-toluenesulfonoxy)-1-indanone

2-methyl-4-benzenesulfonoxy-1-indanone

2-methyl-4-(2,4,6-triisopropylbenzenesulfonoxy)-1-indanone

2-methyl-4-pentafluorobenzenesulfonoxy-1-indanone

2-methyl-4-nonafluorobutanesulfonoxy-1-indanone

2-methyl-4-acetoxy-1-indanone

2-methyl-4-formyloxy-1-indanone

2-methyl-4-pentafluorobenzoyloxy-1-indanone

2-methyl-4-(p-nitrobenzoyloxy)-1-indanone

2-methyl-4-methoxycarbonyloxy-1-indanone

2-methyl-4-tert-butyloxycarbonyloxy-1-indanone

2-methyl-4-ethoxycarbonyloxy-1-indanone

2-methyl-4-benzyloxycarbonyloxy-1-indanone

2-methyl-4-dimethylphosphonoxy-1-indanone

2-methyl-4-diethylphosphonoxy-1-indanone

2-methyl-4-diphenylphosphonoxy-1-indanone

2-methyl-4-diazonium-1-indanone chloride

2-methyl-4-diazonium-1-indanone tetrafluoroborate

2-methyl-4-diazonium-1-indanone sulfate

2-methyl-7-vinyl-4-bromo-1-indanone

2-methyl-5-butyl-4-bromo-1-indanone

2-methyl-6-fluoro-4-bromo-1-indanone

2-methyl-7-isopropyl-4-bromo-1-indanone

2-methyl-4,7-dibromo-1-indanone

2-methyl-5,4-dichloro-1-indanone

2-methyl-6,4-dichloro-1-indanone

2-methyl-4,7-dichloro-1-indanone

2-methyl-5-chloro-4-bromo-1-indanone

2-methyl-7-phenyl-4-diazonium-1-indanone chloride

2-methyl-7-cyclohexyl-4-diazonium-1-indanone tetrafluoroborate

2,5-dimethyl-4-chloro-1-indanone

2,7-dimethyl-4-bromo-1-indanone

2,6-dimethyl-4-chloro-1-indanone

2-methyl-5-butyl-4-chloro-1-indanone

2-methyl-5-isopropyl-4-trifluoromethanesulfonoxy-1-indanone

2-methyl-5-tert-butyl-4-methanesulfonoxy-1-indanone

2-methyl-5-phenyl-4-bromo-1-indanone

2-methyl-5-(3,5-dimethoxyphenyl)-4-iodo-1-indanone

2-methyl-6-benzyl-4-chloro-1-indanone

2-methyl-6-methoxy-4-chloro-1-indanone

2-methyl-5-phenoxy-4-chloro-1-indanone

2-methyl-6-methoxy-4-chloro-1-indanone

2-methyl-6-isopropoxy-4-bromo-1-indanone

2-methyl-6-trimethylsilyloxy-4-bromo-1-indanone

2-methyl-5-vinyl-4-(p-toluenesulfonoxy)-1-indanone

2-methyl-6-bromo-4-trifluoroacetoxy-1-indanone

2-methyl-6-phenyl-4-bromo-1-indanone

2-methyl-7-methoxy-4-chloro-1-indanone

2-methyl-7-diisopropylamino-4-chloro-1-indanone

2-trifluoromethyl-4-chloro-1-indanone

2-trifluoromethyl-4-bromo-1-indanone

2-trifluoromethyl-4-methyl-4-chloro-1-indanone

2-trifluoromethyl-5-isobutyl-4-trifluoromethanesulfonoxy-1-indanone

2-ethyl-4-chloro-1-indanone

2-ethyl-4-bromo-1-indanone

2-ethyl-4-diazonium-1-indanone tetrafluoroborate

2-ethyl-4-methanesulfonoxy-1-indanone

2-ethyl-5-trimethylsilyloxy-4-trifluoromethanesulfonoxy-1-indanone

2-ethyl-5-methyl-4-bromo-1-indanone

2-ethyl-7-benzyl-4-bromo-1-indanone

2-ethyl-4-diazonium-1-indanone tetrafluoroborate

2,6-diethyl-4-diazonium-1-indanone chloride

2-n-propyl-4-chloro-1-indanone

2-n-propyl-4-bromo-1-indanone

2-n-propyl-4,6-dichloro-1-indanone

2-n-propyl-7-trifluoromethanesulfonoxy-1-indanone

2-butyl-4-chloro-1-indanone

2-butyl-4-bromo-1-indanone

2-butyl-5-fluoro-4-chloro-1-indanone

2-butyl-4,5-dichloro-1-indanone

2-isopropyl-4-chloro-1-indanone

2-isopropyl-4-bromo-1-indanone

2-isopropyl-4-iodo-1-indanone

2-isopropyl-5-diphenylphosphino-4-nonafluorobutanesulfonoxy-1-indanone

2-phenyl-7-dimethylamino-4-bromo-1-indanone

2-phenyl-4-chloro-1-indanone

2-(2-pyridyl)-4-bromo-1-indanone

2-(2-furyl)-4-iodo-1-indanone

2-cyclohexyl-4-chloro-1-indanone

2-cyclohexyl-4-bromo-1-indanone

2-cyclohexyl-4-trifluoromethanesulfonoxy-1-indanone

2-isobutyl-4-chloro-1-indanone

2-isobutyl-4-bromo-1-indanone

2-tert-butyl-4-chloro-1-indanone

2-tert-butyl-4-iodo-1-indanone

2-benzyl-4-chloro-1-indanone

2-allyl-4-chloro-1-indanone

2-vinyl-4-trifluoromethanesulfonoxy-1-indanone

2-(2-trimethylsilylethyn-1-yl)-6-benzyl-4-chloroindanone

2-(hex-1-ynyl)-4-trifluoromethanesulfonoxy-1-indanone

2-trimethylsilyl-4-bromo-1-indanone

2-trimethylsilyloxy-4-bromo-1-indanone

2-dimethylamino-4-trifluoromethanesulfonoxy-1-indanone

2-N-pyrrolidino-4-chloro-1-indanone

2-diphenylphosphino-5-isopropyl-4-bromo-1-indanone

2-methoxy-6-allyl-4-chloro-1-indanone

2,6-dimethoxy-4-bromo-1-indanone

2-phenoxy-5-dimethylamino-4-trifluoromethanesulfonoxy-1-indanone

2-(2-methoxyethyl)-4-chloro-1-indanone

2-(3-chloropropyl)-4-chloro-1-indanone

2,5,6,7-tetramethyl-4-chloro-1-indanone

2-methyl-7-phenyl-5-methoxy-4-bromo-1-indanone

2-butyl-5-benzyl-6-bromo-4-trifluoromethanesulfonoxy-1-indanone

2-trimethylsilyloxy-7-methoxy-5-allyl-4-diazonium-1-indanonetetrafluoroborate

2-N-piperidino-7-fluoro-5,4-dibromo-1-indanone

2-isopropyl-7-cyclohexyl-5-methyl-4-trimethylstannyl-1-indanone

2,5-dimethoxy-7-bromo-6-trifluoromethyl-4-iodo-1-indanone

2-ethyl-7-dimethylamino-5-trimethylsilyl-4-chloroindanone

2-trifluoroethoxy-7-thiomethoxy-6-butyl-4-bromo-1-indanone

2-triethylsilyl-5,6-difluoro-4-methanesulfonoxy-1-indanone

2,5-diphenyl-4-bromo-1-indanone

Illustrative examples of indanones of the formula II, which, however, donot restrict the scope of the invention, are:

2-methyl-7-phenyl-1-indanone

2-methyl-7-(1-naphthyl)-1-indanone

2-methyl-6-(2-naphthyl)-1-indanone

2-methyl-7-(2-methyl-1-naphthyl)-1-indanone

2-methyl-7-(4-methyl-1-naphthyl)-1-indanone

2-methyl-7-(4-methoxy-1-naphthyl)-1-indanone

2-methyl-7-(6-methoxy-2-naphthyl)-1-indanone

2-methyl-7-(4-methylphenyl)-1-indanone

2-methyl-7-(3-methylphenyl)-1-indanone

2-methyl-7-(2-methylphenyl-1-indanone

2-methyl-7-(3,5-dimethylphenyl)-1-indanone

2-methyl-7-(2,3-dimethylphenyl)-1-indanone

2-methyl-7-(2,4-dimethylphenyl)-1-indanone

2-methyl-7-(2,5-dimethylphenyl)-1-indanone

2-methyl-7-(3-butylphenyl)-1-indanone

2-methyl-7-(4-tert-butylphenyl)-1-indanone

2-methyl-7-(4-ethylphenyl)-1-indanone

2-methyl-7-(4-isopropylphenyl)-1-indanone

2-methyl-7-(3,5-di-tert-butylphenyl)-1-indanone

2-methyl-7-mesityl-1-indanone

2-methyl-7-(4-biphenyl)-1-indanone

2-methyl-7-(3-biphenyl)-1-indanone

2-methyl-7-(2-biphenyl)-1-indanone

2-methyl-7-(3,5-diphenylphenyl)-1-indanone

2-methyl-7-(4-styryl)-1-indanone

2-methyl-7-(3-styryl)-1-indanone

2-methyl-7-(2-styryl)-1-indanone

2-methyl-7-(9-anthracenyl)-1-indanone

2-methyl-7-(9-phenanthrenyl)-1-indanone

2-methyl-7-(2-hydroxyphenyl)-1-indanone

2-methyl-7-(4-hydroxyphenyl)-1-indanone

2-methyl-7-(3-hydroxyphenyl)-1-indanone

2-methyl-7-(2,4-dihydroxyphenyl)-1-indanone

2-methyl-7-(3,5-dihydroxyphenyl)-1-indanone

2-methyl-7-(4-methoxyphenyl)-1-indanone

2-methyl-7-(3-methoxyphenyl)-1-indanone

2-methyl-7-(2-methoxyphenyl)-1-indanone

2-methyl-7-(2,4-dimethoxyphenyl)-1-indanone

2-methyl-7-(3,5-dimethoxyphenyl)-1-indanone

2-methyl-7-(3,4,5-trimethoxyphenyl)-1-indanone

2-methyl-7-(4-phenoxyphenyl)-1-indanone

2-methyl-7-(3,4-methylenedioxyphenyl)-1-indanone

2-methyl-7-(4-thioanisyl)-1-indanone

2-methyl-7-(3-thioanisyl)-1-indanone

2-methyl-7-(4-nitrophenyl)-1-indanone

2-methyl-7-(3-nitrophenyl)-1-indanone

2-methyl-7-(2-nitrophenyl)-1-indanone

2-methyl-7-(4-methyl-3-nitrophenyl)-1-indanone

2-methyl-7-(4-methoxycarbonylphenyl)-1-indanone

2-methyl-7-(3-methoxycarbonylphenyl)-1-indanone

2-methyl-7-(2-methoxycarbonylphenyl)-1-indanone

2-methyl-7-(4-carboxyphenyl)-1-indanone

2-methyl-7-(2-carboxyphenyl)-1-indanone

2-methyl-7-(4-formylphenyl)-1-indanone

2-methyl-7-(4-acetylphenyl)-1-indanone

2-methyl-7-(4-pivaloylphenyl)-1-indanone

2-methyl-7-(4-aminophenyl)-1-indanone

2-methyl-7-(3-aminophenyl)-1-indanone

2-methyl-7-(2-aminophenyl)-1-indanone

2-methyl-7-(4-dimethylaminophenyl)-1-indanone

2-methyl-7-(3-dimethylaminophenyl)-1-indanone

2-methyl-7-(4-(1-pyrrolidino)phenyl)-1-indanone

2-methyl-7-(4-hydrazinophenyl)-1-indanone

2-methyl-7-(4-cyanophenyl)-1-indanone

2-methyl-7-(3-cyanophenyl)-1-indanone

2-methyl-7-(2-cyanophenyl)-1-indanone

2-methyl-7-(4-trifluoromethoxyphenyl)-1-indanone

2-methyl-7-(4-fluorophenyl)-1-indanone

2-methyl-7-(4-bromophenyl)-1-indanone

2-methyl-7-(2,4-difluorophenyl)-1-indanone

2-methyl-7-(4-chlorophenyl)-1-indanone

2-methyl-7-(3,5-dichlorophenyl)-1-indanone

2-methyl-7-(4-trifluoromethylphenyl)-1-indanone

2-methyl-7-(3-trifluoromethylphenyl)-1-indanone

2-methyl-7-(3,5-bis(trifluoromethyl)phenyl)-1-indanone

2-methyl-7-(2,4-bis(trifluoromethyl)phenyl)-1-indanone

2-methyl-7-(2-furyl)-1-indanone

2-methyl-7-(3-furyl)-1-indanone

2-methyl-7-(5-methyl-2-furyl)-1-indanone

2-methyl-7-(benzofuryl)-1-indanone

2-methyl-7-(2-thiophenyl)-1-indanone

2-methyl-7-(5-methyl-2-thiophenyl)-1-indanone

2-methyl-7-(3-thiophenyl)-1-indanone

2-methyl-7-(5-isobutyl-2-thiophenyl)-1-indanone

2-methyl-7-(benzothiophenyl)-1-indanone

2-methyl-7-(N-methyl-2-pyrrolyl)-1-indanone

2-methyl-7-(N-methyl-3-pyrrolyl)-1-indanone

2-methyl-7-(2-pyridyl)-1-indanone

2-methyl-7-(3-pyridyl)-1-indanone

2-methyl-7-(4-pyridyl)-1-indanone

2-methyl-7-(2-pyrimidyl)-1-indanone

2-methyl-7-(2-quinolyl)-1-indanone

2-methyl-7-(3-quinolyl)-1-indanone

2-methyl-7-(4-isoquinolyl)-1-indanone

2-methyl-7-(2-thiazolyl)-1-indanone

2-methyl-7-(2-benzothiazolyl)-1-indanone

2-methyl-7-(2-N-methylimidazolyl)-1-indanone

2-methyl-7-(2-N-methylbenzoimidazolyl)-1-indanone

2-methyl-7-(2-oxazolyl)-1-indanone

2-methyl-7-(N-methyltriazolyl)-1-indanone

2-methyl-7-butyl-1-indanone

2-methyl-7-cyclohexyl-1-indanone

2-methyl-7-isopropyl-1-indanone

2-methyl-7-benzyl-1-indanone

2-methyl-7-(hex-1-en-6-yl)-1-indanone

2-methyl-7-(hex-1-en-1-yl)-1-indanone

2-methyl-7-vinyl-1-indanone

2-methyl-7-(2-trimethylsilylethen-1-yl)-1-indanone

2-methyl-7-(2-phenylethyn-1-yl)-1-indanone

2-methyl-7-(2-tert-butylethyn-1-yl)-1-indanone

2-methyl-7-allyl-1-indanone

2-methyl-7-(2-trimethylsilylethyn-1-yl)-1-indanone

2-methyl-7-(2-phenylethen-1-yl)-1-indanone

2-methyl-7-trimethylstannyl-1-indanone

2-methyl-7-tributylstannyl-1-indanone

2-methyl-7-triphenylstannyl-1-indanone

2-methyl-7-(boronic acid pinacol ester)-1-indanone

2-methyl-7-(boronic acid trimethylene glycol ester)-1-indanone

2-methyl-7-(B-catecholborane)-1-indanone

2-methyl-7-diphenylphosphino-1-indanone

2-methyl-7-dibutylphosphino-1-indanone

2-methyl-7-(methoxyphenylmethylphosphino)-1-indanone

2-ethyl-7-phenyl-1-indanone

2-ethyl-7-(4-tolyl)-1-indanone

2-ethyl-7-naphthyl-1-indanone

2-ethyl-7-(2-furyl)-1-indanone

2-ethyl-7-cyclohexyl-1-indanone

2-ethyl-7-(4-tert-butylphenyl)-1-indanone

2-n-propyl-7-phenyl-1-indanone

2-n-propyl-7-naphthyl-1-indanone

2-n-propyl-7-(4-tert-butylphenyl)-1-indanone

2-n-propyl-7-(4-methylphenyl)-1-indanone

2-n-butyl-7-phenyl-1-indanone

2-n-butyl-7-naphthyl-1-indanone

2-n-butyl-7-(4-tert-butylphenyl)-1-indanone

2-n-butyl-7-(4-methylphenyl)-1-indanone

2-isopropyl-7-(2-pyrridyl)-1-indanone

2-isopropyl-7-phenyl-1-indanone

2-isopropyl-7-naphthyl-1-indanone

2-isobutyl-7-phenyl-1-indanone

2-isobutyl-7-naphthyl-1-indanone

2-cyclohexyl-7-phenyl-1-indanone

2-trifluoromethyl-7-phenyl-1-indanone

2-trifluoromethyl-7-(4-tolyl)-1-indanone

2-trifluoromethyl-7-naphthyl-1-indanone

2-trifluoromethyl-7-(4-methoxyphenyl)-1-indanone

2-trifluoromethyl-7-(3,5-bis(trifluoromethyl)phenyl)-1-indanone

2,4-dimethyl-7-phenyl-1-indanone

2-methyl-4-methoxy-7-phenyl-1-indanone

2,6-dimethyl-7-phenyl-1-indanone

2,5-dimethyl-7-phenyl-1-indanone

2,5-dimethyl-7-p-tolyl-1-indanone

2,5-dimethyl-7-(2-thiophenyl)-1-indanone

2,4-methyl-7-naphthyl-1-indanone

2-methyl-5-phenyl-7-naphthyl-1-indanone

2-methyl-5,7-diphenyl-1-indanone

2-methyl-7-(4-fluorophenyl)-1-indanone

2-methyl-5-diphenylphosphino-7-(4-nitrophenyl)-1-indanone

2-methyl-5-chloro-7-phenyl-1-indanone

2,6-dimethyl-7-(4-methoxyphenyl)-1-indanone

2-ethyl-4-methyl-7-(3,5-bis(trifluoromethyl)phenyl)-1-indanone

2-ethyl-5-vinyl-7-(2-furyl)-1-indanone

2-isopropyl-5-trifluoromethyl-7-phenyl-1-indanone

2-cyclohexyl-5-methyl-7-(2-pyridyl)-1-indanone

2-trifluoromethyl-4-butyl-7-naphthyl-1-indanone

2,5-trifluoromethyl-7-butyl-1-indanone

2-trimethylsilyl-5-isopropyl-7-(boronic acid pinacol ester)-1-indanone

2-dimethylamino-6-cyclohexyl-7-trimethylstannyl-1-indanone

2,4,5,6-tetramethyl-7-phenyl-1-indanone

2-methyl-4-phenyl-5-methoxy-7-naphthyl-1-indanone

2-butyl-5-benzyl-6-bromo-7-(4-methoxyphenyl)-1-indanone

2-trimethylsilyloxy-4-methoxy-5-allyl-7-(2-pyridyl)-1-indanone

2-N-piperidino-4-fluoro-5,7-diphenyl-1-indanone

2-isopropyl-4-cyclohexyl-5-methyl-7-trimethylstannyl-1-indanone

2,5-dimethoxy-4-bromo-6-trifluoromethyl-7-furyl-1-indanone

2-ethyl-5-trimethylsilyl-7-(2-tert-butylethyn-1-yl)-1-indanone

2-trifluoroethoxy-4-thiomethoxy-6-butyl-7-vinyl-1-indanone

2-triethylsilyl-5,6-difluoro-7-(3-cyanophenyl)-1-indanone

2,5-diphenyl-7-fluoro-1-indanone

Illustrative examples of indanones of the formula IIa, which, however,do not restrict the scope of the invention, are:

2-methyl-4-phenyl-1-indanone

2-methyl-4-(1-naphthyl)-1-indanone

2-methyl-4-(2-naphthyl)-1-indanone

2-methyl-4-(2-methyl-1-naphthyl)-1-indanone

2-methyl-4-(4-methyl-1-naphthyl)-1-indanone

2-methyl-4-(4-methoxy-1-naphthyl)-1-indanone

2-methyl-4-(6-methoxy-2-naphthyl)-1-indanone

2-methyl-4-(4-methylphenyl)-1-indanone

2-methyl-4-(3-methylphenyl)-1-indanone

2-methyl-4-(2-methylphenyl)-1-indanone

2-methyl-4-(3,5-dimethylphenyl)-1-indanone

2-methyl-4-(2,3-dimethylphenyl)-1-indanone

2-methyl-4-(2,4-dimethylphenyl)-1-indanone

2-methyl-4-(2,5-dimethylphenyl)-1-indanone

2-methyl-4-(3-butylphenyl)-1-indanone

2-methyl-4-(4-tert-butylphenyl)-1-indanone

2-methyl-4-(3,5-di-tert-butylphenyl)-1-indanone

2-methyl-4-mesityl-1-indanone

2-methyl-4-(4-biphenyl)-1-indanone

2-methyl-4-(3-biphenyl)-1-indanone

2-methyl-4-(2-biphenyl)-1-indanone

2-methyl-4-(3,5-diphenylphenyl)-1-indanone

2-methyl-4-(4-styryl)-1-indanone

2-methyl-4-(3-styryl)-1-indanone

2-methyl-4-(2-styryl)-1-indanone

2-methyl-4-(9-anthracenyl)-1-indanone

2-methyl-4-(9-phenanthrenyl)-1-indanone

2-methyl-4-(2-hydroxyphenyl)-1-indanone

2-methyl-4-(4-hydroxyphenyl)-1-indanone

2-methyl-4-(3-hydroxyphenyl)-1-indanone

2-methyl-4-(2,4-dihydroxyphenyl)-1-indanone

2-methyl-4-(3,5-dihydroxyphenyl)-1-indanone

2-methyl-4-(4-methoxyphenyl)-1-indanone

2-methyl-4-(3-methoxyphenyl)-1-indanone

2-methyl-4-(2-methoxyphenyl)-1-indanone

2-methyl-4-(2,4-dimethoxyphenyl)-1-indanone

2-methyl-4-(3,5-dimethoxyphenyl)-1-indanone

2-methyl-4-(3,4,5-trimethoxyphenyl)-1-indanone

2-methyl-4-(4-phenoxyphenyl)-1-indanone

2-methyl-4-(3,4-methylenedioxyphenyl)-1-indanone

2-methyl-4-(4-thioanisyl)-1-indanone

2-methyl-4-(3-thioanisyl)-1-indanone

2-methyl-4-(4-nitrophenyl)-1-indanone

2-methyl-4-(3-nitrophenyl)-1-indanone

2-methyl-4-(2-nitrophenyl)-1-indanone

2-methyl-4-(4-methyl-3-nitrophenyl)-1-indanone

2-methyl-4-(4-methoxycarbonylphenyl)-1-indanone

2-methyl-4-(3-methoxycarbonylphenyl)-1-indanone

2-methyl-4-(2-methoxycarbonylphenyl)-1-indanone

2-methyl-4-(4-carboxylphenyl)-1-indanone

2-methyl-4-(2-carboxylphenyl)-1-indanone

2-methyl-4-(4-formylphenyl)-1-indanone

2-methyl-4-(4-acetylphenyl)-1-indanone

2-methyl-4-(4-pivaloylphenyl)-1-indanone

2-methyl-4-(4-aminophenyl)-1-indanone

2-methyl-4-(3-aminophenyl)-1-indanone

2-methyl-4-(2-aminophenyl)-1-indanone

2-methyl-4-(4-dimethylaminophenyl)-1-indanone

2-methyl-4-(3-dimethylaminophenyl)-1-indanone

2-methyl-4-(4-(1-pyrrolidino)phenyl)-1-indanone

2-methyl-4-(4-hydrazinophenyl)-1-indanone

2-methyl-4-(4-cyanophenyl)-1-indanone

2-methyl-4-(3-cyanophenyl)-1-indanone

2-methyl-4-(2-cyanophenyl)-1-indanone

2-methyl-4-(4-trifluoromethoxyphenyl)-1-indanone

2-methyl-4-(4-fluorophenyl)-1-indanone

2-methyl-4-(4-bromophenyl)-1-indanone

2-methyl-4-(2,4-difluorophenyl)-1-indanone

2-methyl-4-(4-chlorophenyl)-1-indanone

2-methyl-4-(3,5-dichlorophenyl)-1-indanone

2-methyl-4-(4-trifluoromethylphenyl)-1-indanone

2-methyl-4-(3-trifluoromethylphenyl)-1-indanone

2-methyl-4-(3,5-bis(trifluoromethyl)phenyl)-1-indanone

2-methyl-4-(2,4-bis(trifluoromethyl)phenyl)-1-indanone

2-methyl-4-(2-furyl)-1-indanone

2-methyl-4-(3-furyl)-1-indanone

2-methyl-4-(5-methyl-2-furyl)-1-indanone

2-methyl-4-(benzofuryl)-1-indanone

2-methyl-4-(2-thiophenyl)-1-indanone

2-methyl-4-(5-methyl-2-thiophenyl)-1-indanone

2-methyl-4-(3-thiophenyl)-1-indanone

2-methyl-4-(5-isobutyl-2-thiophenyl)-1-indanone

2-methyl-4-(benzothiophenyl)-1-indanone

2-methyl-4-(N-methyl-2-pyrrolyl)-1-indanone

2-methyl-4-(N-methyl-3-pyrrolyl)-1-indanone

2-methyl-4-(2-pyridyl)-1-indanone

2-methyl-4-(3-pyridyl)-1-indanone

2-methyl-4-(4-pyridyl)-1-indanone

2-methyl-4-(2-pyrimidyl)-1-indanone

2-methyl-4-(2-quinolyl)-1-indanone

2-methyl-4-(3-quinolyl)-1-indanone

2-methyl-4-(4-isoquinolyl)-1-indanone

2-methyl-4-(2-thiazolyl)-1-indanone

2-methyl-4-(2-benzothioazolyl)-1-indanone

2-methyl-4-(2-N-methylimidazolyl)-1-indanone

2-methyl-4-(2-N-methylbenzoimidazolyl)-1-indanone

2-methyl-4-(2-oxazolyl)-1-indanone

2-methyl-4-(N-methyltriazolyl)-1-indanone

2-methyl-4-butyl-1-indanone

2-methyl-4-cyclohexyl-1-indanone

2-methyl-4-isopropyl-1-indanone

2-methyl-4-benzyl-1-indanone

2-methyl-4-(hex-1-en-6-yl)-1-indanone

2-methyl-4-(hex-1-en-1-yl)-1-indanone

2-methyl-4-vinyl-1-indanone

2-methyl-4-(2-trimethylsilylethen-1-yl)-1-indanone

2-methyl-4-(2-phenylethyn-1-yl)-1-indanone

2-methyl-4-(2-tert-butylethyn-1-yl)-1-indanone

2-methyl-4-allyl-1-indanone

2-methyl-4-(2-trimethylsilylethyn-1-yl)-1-indanone

2-methyl-4-(2-phenylethen-1-yl)-1-indanone

2-methyl-4-trimethylstannyl-1-indanone

2-methyl-4-tributylstannyl-1-indanone

2-methyl-4-triphenylstannyl-1-indanone

2-methyl-4-(boronic acid pinacol ester)-1-indanone

2-methyl-4-(boronic acid trimethylene glycol ester)-1-indanone

2-methyl-4-(B-catecholborane)-1-indanone

2-methyl-4-diphenylphosphino-1-indanone

2-methyl-4-dibutylphosphino-1-indanone

2-methyl-4-(methoxyphenyl-methyl-phosphino)-1-indanone

2-ethyl-4-phenyl-1-indanone

2-ethyl-4-(4-tolyl)-1-indanone

2-ethyl-4-naphthyl-1-indanone

2-ethyl-4-(2-furyl)-1-indanone

2-ethyl-4-cyclohexyl-1-indanone

2-ethyl-4-butyl-1-indanone

2-n-propyl-4-phenyl-1-indanone

2-n-propyl-4-naphthyl-1-indanone

2-n-propyl-7-(4-tert-butylphenyl)-1-indanone

2-n-propyl-7-(4-methylphenyl)-1-indanone

2-n-butyl-7-phenyl-1-indanone

2-n-butyl-7-naphthyl-1-indanone

2-n-butyl-7-(4-tert-butylphenyl)-1-indanone

2-n-butyl-7-(4-methylphenyl)-1-indanone

2-isopropyl-4-(2-pyrridyl)-1-indanone

2-isopropyl-4-phenyl-1-indanone

2-isopropyl-4-naphthyl-1-indanone

2-isobutyl-4-phenyl-1-indanone

2-isobutyl-4-naphthyl-1-indanone

2-cyclohexyl-4-phenyl-1-indanone

2-trifluoromethyl-4-phenyl-1-indanone

2-trifluoromethyl-4-(4-tolyl)-1-indanone

2-trifluoromethyl-4-naphthyl-1-indanone

2-trifluoromethyl-4-(4-methoxyphenyl)-1-indanone

2-trifluoromethyl-4-(3,5-bis(trifluoromethyl)phenyl)-1-indanone

2,7-dimethyl-4-phenyl-1-indanone

2-methyl-7-methoxy-4-phenyl-1-indanone

2,6-dimethyl-4-phenyl-1-indanone

2,5-dimethyl-4-phenyl-1-indanone

2,5-dimethyl-4-p-tolyl-1-indanone

2,5-dimethyl-4-(2-thiophenyl)-1-indanone

2,7-methyl-4-naphthyl-1-indanone

2-methyl-5-phenyl-4-naphthyl-1-indanone

2-methyl-5,4-diphenyl-1-indanone

2-methyl-4-(4-fluorophenyl)-1-indanone

2-methyl-5-diphenylphosphino-4-(4-nitrophenyl)-1-indanone

2-methyl-5-chloro-4-phenyl-1-indanone

2,6-dimethyl-4-(4-methoxyphenyl)-1-indanone

2-ethyl-7-methyl-4-(3,5-bis(trifluoromethyl)phenyl)-1-indanone

2-ethyl-5-vinyl-4-(2-furyl)-1-indanone

2-isopropyl-5-trifluoromethyl-4-phenyl-1-indanone

2-cyclohexyl-5-methyl-4-(2-pyridyl)-1-indanone

2-trifluoromethyl-7-butyl-4-naphthyl-1-indanone

2,5-trifluoromethyl-4-butyl-1-indanone

2-trimethylsilyl-5-isopropyl-4-(boronic acid pinacol ester)-1-indanone

2-dimethylamino-6-cyclohexyl-4-trimethylstannyl-1-indanone

2,5,6,7-tetramethyl-4-phenyl-1-indanone

2-methyl-7-phenyl-5-methoxy-4-naphthyl-1-indanone

2-butyl-5-benzyl-6-bromo-4-(4-methoxyphenyl)-1-indanone

2-trimethylsilyloxy-7-methoxy-5-allyl-4-(2-pyridyl)-1-indanone

2-N-piperidino-7-fluoro-5,4-diphenyl-1-indanone

2-isopropyl-7-cyclohexyl-5-methyl-4-trimethylstannyl-1-indanone

2,5-dimethoxy-7-bromo-6-trifluoromethyl-4-furyl-1-indanone

2-trifluoroethoxy-7-thiomethoxy-6-butyl-4-vinyl-1-indanone

2-triethylsilyl-5,6-difluoro-4-(3-cyanophenyl)-1-indanone

2,5-diphenyl-7-fluoro-1-indanone

In the process of the present invention, at least one indanone of theformula I or Ia is reacted with at least one coupling component, formingthe indanones of the formulae II and IIa. In this reaction, the couplingcomponent serves to introduce the radical R³. It is also possible forthe coupling component to convert one or more of the radicals Y¹, Y² andY³ which are as defined for X into radicals Y⁴, Y⁵ and Y⁶ which are asdefined for R³.

The coupling components are preferably compounds containing elements ofGroups 13-17 of the Periodic Table of the Elements. The couplingcomponents are preferably compounds containing boron, carbon, silicon,germanium, tin, phosphorus or fluorine. The coupling components areparticularly preferably compounds containing boron, carbon, silicon, tinor phosphorus.

Preferred boron-containing coupling components are boronic acids andboronic esters, for example of the typeR⁴—B(OR⁵)₂,where R⁴ is a C₁-C₄₀-group such as a linear, branched or cyclicC₁-C₂₀-alkyl group which may bear one or more identical or differenthalogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents,a C₆-C₂₂-aryl group which may bear one or more identical or differenthalogen, OR², SR², NR² ₂—, NH₂, —N₂H₃, NO₂, CN, CO₂R², COR² ₄, CHO, PR²₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₇-C₁₅-alkylaryl group orC₇-C₁₅-arylalkyl group, where the alkyl group may bear one or moreidentical or different halogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents and the aryl group may bear one or more identicalor different halogen, OR², SR², NR² ₂—, NH₂, —N₂H₃, NO₂, CN, CO₂R²,COR², CHO, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₂-C₁₀-alkenylgroup which may bear one or more identical or different halogen, OH,OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, aC₂-C₁₀-alkynyl group which may bear one or more identical or differenthalogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents,a C₈-C₁₂-arylalkenyl group which may bear one or more identical ordifferent halogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents, or R⁴ is a C₁-C₂₀-heterocyclic group which may in turnbear C₁-C₂₀-radicals or heteroatoms as substituents, and

R⁵ are identical or different and may each be a hydrogen atom, a linear,branched or cyclic C₁-C₄₀-group, for example a C₁-C₂₀-alkyl group or aC₆-C₁₄-aryl group, or form a ring system. Also preferred arecondensation products of the above-mentioned boronic acids and boronicesters.

Preferred boron-containing coupling components are, furthermore,boranes, for example of the type R⁶—B(R⁷)₂, where R⁶ is a linear,branched or cyclic C₁-C₂₀-alkyl group or a C₆-C₁₄-aryl group, which mayeach bear one or more identical or different halogen, OR², SR², NR² ₂—,NH₂, —N₂H₃, NO₂, CN, CO₂R², COR², CHO, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents, and R⁷ are identical or different and are each halogen, alinear, branched or cyclic C₁-C₄₀-group, for example a C₁-C₂₀-alkylgroup or a C₆-C₁₄-aryl group, or R⁷ form a ring system.

Also preferred are diboranes, for example of the type

where R⁵ is as defined above, in particular the compounds

Examples of carbon-containing coupling components are alkenes andalkynes. Particular preference is given to alkenes and alkynes of theformula

R, R′ and R″ are identical or different and are each H or a C₁-C₁₀-alkylgroup, where one or more of the CH₂ groups may be replaced by identicalor different O, S, NR², —CO—, —OC═O—, C(O)O, —CONR², C₆-C₁₄-arylene—CH₂═CH₂—, —C≡C— or —SiR² groups and one or more H of R may be replacedby identical or different C₁-C₄-alkyl, OH, SiR₃ ², halogen, —C≡N—, —N₃,NR₂ ², COOH, —CO₂R² or —OC(O)R² substituents, where R, R′ and R″ mayform one or more ring systems and R² is as defined in formula I.

Very particular preference is given to alkenes and alkynes in which R,R′ are identical or different and are each H or a C₁-C₆-alkyl group,where one or two CH₂ groups may be replaced by identical or different—CO—, —C(O)O—, CONR² and phenylene groups and from 1 to 3 H of R may bereplaced by identical or different SiR₃ ², OH, F, Cl, CN and CO₂R²substituents, and in which R″ is H and R² is as defined above.

Examples of silicon-containing coupling components are compounds of thetype R⁴—Si(R⁷)₃ with the abovementioned definitions for R⁴ and R⁷.

Examples of tin-containing coupling components are stannanes, forexample of the type R⁴—Sn(R⁷)₃, and also distannanes of the type(R⁷)₃Sn—Sn(R⁷)₃ with the abovementioned definitions for R⁴ and R⁷.

Examples of phosphorus-containing coupling components are compounds ofthe type (R⁵)₂P—R⁸, where the radical R⁸ is H, Sn(R⁷)₃ or Si(R⁷)₃ and R⁵and R⁷ are as defined above.

Examples of fluorine-containing coupling components are fluoride saltsin which the cation is an element of groups 1-3 of the Periodic Table ofthe Elements or, particularly preferably, is a bulky peralkylatedammonium, sulfonium, amidosulfonium, phosphonium, amidophosphonium orguanidinium cation.

The coupling components described are illustrated by the followingexamples which do not restrict the scope of the invention.

Examples of boronic acids and boronic esters are:

phenylboronic acid

p-tolylboronic acid

m-tolylboronic acid

o-tolylboronic acid

2,3-dimethylphenylboronic acid

2,4-dimethylphenylboronic acid

2,6-dimethylphenylboronic acid

3,5-dimethylphenylboronic acid

mesitylboronic acid

tetramethylphenylboronic acid

butylphenylboronic acid

4-tert-butylphenylboronic acid

4-ethylphenylboronic acid

tert-butylphenylboronic acid

isopropylphenylboronic acid

cyclohexylphenylboronic acid

4-(hex-5-en-1-yl)phenylboronic acid triisopropylsilylphenylboronic acid

p-methoxyphenylboronic acid

m-methoxyphenylboronic acid

o-methoxyphenylboronic acid

2,4-dimethoxyphenylboronic acid

2,5-dimethoxyphenylboronic acid

3,5-dimethoxyphenylboronic acid

2,3,4-trimethoxyphenylboronic acid

2,4,6-trimethoxyphenylboronic acid

3,4,5-trimethoxyphenylboronic acid

p-phenoxyphenylboronic acid

p-ethoxyphenylboronic acid

2-(3′-phenylboronic acid)-1,3-dioxolane

3,4-(methylenedioxy)phenylboronic acid

3,4-(isopropylidenedioxy)phenylboronic acid

p-thioanisylboronic acid

m-thioanisylboronic acid

o-thioanisylboronic acid

p-nitrophenylboronic acid

o-nitrophenylboronic acid

m-nitrophenylboronic acid

3-nitro-4-methylphenylboronic acid

3-nitro-4-bromophenylboronic acid

4-(methoxycarbonyl)phenylboronic acid

3-(methoxycarbonyl)phenylboronic acid

2-(methoxycarbonyl)phenylboronic acid

4-carboxylphenylboronic acid

3-carboxylphenylboronic acid

2-carboxylphenylboronic acid

formylphenylboronic acid

acetylphenylboronic acid

pivaloylphenylboronic acid

o-fluorophenylboronic acid

m-fluorophenylboronic acid

p-fluorophenylboronic acid

2,3-difluorophenylboronic acid

2,4-difluorophenylboronic acid

3,5-difluorophenylboronic acid

2,3,4-trifluorophenylboronic acid

2,4,6-trifluorophenylboronic acid

tetrafluorophenylboronic acid

pentafluorophenylboronic acid

o-chlorophenylboronic acid

m-chlorophenylboronic acid

p-chlorophenylboronic acid

3,5-dichlorophenylboronic acid

2,4,6-trichlorophenylboronic acid

p-bromophenylboronic acid

p-trifluoromethylphenylboronic acid

m-trifluoromethylboronic acid

o-trifluoromethylboronic acid

2,6-bis(trifluoromethyl)phenylboronic acid

3,5-bis(trifluoromethyl)phenylboronic acid

p-trifluoromethyltetrafluorophenylboronic acid

trifluoromethoxyphenylboronic acid

o-cyanophenylboronic acid

m-cyanophenylboronic acid

p-cyanophenylboronic acid

tetrafluorocyanophenylboronic acid

m-aminophenylboronic acid

p-aminophenylboronic acid

tetrafluoro-4-aminophenylboronic acid

3-amino-4-methylphenylboronic acid

p-dimethylaminophenylboronic acid

m-dimethylaminophenylboronic acid

o-dimethylaminophenylboronic acid

hydrazylphenylboronic acid

p-hydroxyphenylboronic acid

m-hydroxyphenylboronic acid

o-hydroxyphenylboronic acid

3-hydroxy-4-phenylboronic acid

2,4-dihydroxyphenylboronic acid

3,5-dihydroxyphenylboronic acid

1-naphthylboronic acid

2-naphthylboronic acid

2-methyl-1-naphthylboronic acid

4-methyl-1-naphthylboronic acid

4-methoxy-1-naphthylboronic acid

6-methoxy-2-naphthylboronic acid

2-biphenylboronic acid

3-biphenylboronic acid

4-biphenylboronic acid

3,5-diphenylphenylboronic acid

p-styrylboronic acid

m-styrylboronic acid

o-styrylboronic acid

9-anthraceneboronic acid

9-phenanthreneboronic acid

2-furanboronic acid

3-furanboronic acid

5-methyl-2-furanboronic acid

benzofuranboronic acid

2-thiopheneboronic acid

3-thiopheneboronic acid

5-methyl-2-thiopheneboronic acid

benzothiopheneboronic acid

N-methyl-2-pyrroleboronic acid

N-methyl-3-pyrroleboronic acid

2-pyridineboronic acid

3-pyridineboronic acid

4-pyridineboronic acid

pyrimidineboronic acid

2-quinolineboronic acid

3-quinolineboronic acid

4-isoquinolineboronic acid

tetrafluoropyridineboronic acid

vinylboronic acid

but-2-en-2-ylboronic acid

hexenylboronic acid

cyclohexenylboronic acid

2-phenylethenylboronic acid

6-methoxyhex-1-ene-1-boronic acid

allylboronic acid

benzylboronic acid

p-methoxybenzylboronic acid

ethynylboronic acid

2-trimethylsilylethynylboronic acid

2-phenylethynylboronic acid

hex-1-yne-1-boronic acid

tert-butylacetyleneboronic acid

n-butylboronic acid

cyclohexylboronic acid

isopropylboronic acid

phenylboronic acid dimethyl ester

phenylboronic acid diethyl ester

phenylboronic acid dibutyl ester

phenylboronic acid diisopropyl ester

phenylboronic acid dicyclohexyl ester

phenylboronic acid di-tert-butyl ester

phenylboronic acid diphenyl ester

p-tolylboronic acid dimethyl ester

p-tolylboronic acid diethyl ester

p-tolylboronic acid diisopropyl ester

3,5-dimethylphenylboronic acid dibutyl ester

3,5-bis(trifluoromethyl)phenylboronic acid methyl ester

1-naphthylboronic acid dimethyl ester

1-naphthylboronic acid diethyl ester

1-naphthylboronic acid dibutyl ester

1-naphthylboronic acid diisopropyl ester

1-naphthylboronic acid diphenyl ester

2-naphthylboronic acid dimethyl ester

2-naphthylboronic acid diisopropyl ester

2-furanboronic acid dimethyl ester

3-furanboronic acid diisopropyl ester

2-thiopheneboronic acid dimethyl ester

n-methylpyrrole-2-boronic acid diisopropyl ester

pyridineboronic acid dimethyl ester

pyridineboronic acid diisopropyl ester

B-n-butylcatecholborane

B-(1-hexenyl)catecholborane

B-cyclohexylcatecholborane

B-phenylcatecholborane

B-(1-naphthyl)catecholborane

B-(2-naphthyl)catecholborane

B-ethynylcatecholborane

B-(2-trimethylsilylethynyl)catecholborane

B-(2-phenylethynyl)catecholborane

B-(hex-1-yn-1-yl)catecholborane

B-(tert-butylethynyl)catecholborane

phenylboronic acid pinacol ester

phenylboronic acid cyclohexanediol ester

phenylboronic acid trimethylene glycol ester

phenylboronic acid glycol ester

phenylboronic acid 2′,2′-dimethylpropanediol ester

1-naphthylboronic acid cyclohexanediol ester

1-naphthylboronic acid trimethylene glycol ester

1-naphthylboronic acid pinacol ester

1-naphthylboronic acid glycol ester

2-naphthylboronic acid trimethylene glycol ester

2-naphthylboronic acid pinacol ester

methoxyphenylboronic acid dimethyl ester

aminophenylboronic acid tributyl ester

nitrophenylboronic acid pinacol ester

fluorophenylboronic acid trimethylene glycol ester

chlorophenylboronic acid diisopropyl ester

bromophenylboronic acid pinacol ester

cyanophenylboronic acid pinacol ester

4-(methoxycarbonyl)phenylboronic acid pinacol ester

4-(methoxycarbonyl)phenylboronic acid trimethylene glycol ester

vinylboronic acid dimethyl ester

B-vinylcatecholborane

vinylboronic acid trimethylene glycol ester

hex-1-en-1-ylboronic acid diisopropyl ester

B-hexenylcatecholborane

cyclohexenylboronic acid diethyl ester

B-cyclohexenylcatecholborane

2-phenylethenylboronic acid diphenyl ester

2-phenylethenylcatecholborane

6-methoxyhex-1-ene-1-boronic acid dimethyl ester

allylboronic acid diisopropyl ester

allylboronic acid pinacol ester

allylcatecholborane

benzylboronic acid diisopropyl ester

p-methoxybenzylboronic acid trimethylene glycol ester

ethynylboronic acid diisopropyl ester

2-trimethylsilylethynylboronic acid diisopropyl ester

2-trimethylsilylethynylboronic acid trimethylene glycol ester

2-phenylethynylboronic acid pinacol ester

2-phenylethynylboronic acid diisopropyl ester

hex-1-yn-1-boronic acid diisopropyl ester

hex-1-yn-1-boronic acid dibutyl ester

tert-butylacetyleneboronic acid diisopropyl ester

tert-butylacetyleneboronic acid pinacol ester

n-butylboronic acid dimethyl ester

n-butylboronic acid diisopropyl ester

B-n-butylcatecholborane

n-butylboronic acid trimethylene glycol ester

n-butylboronic acid pinacol ester

cyclohexylboronic acid dimethyl ester

B-cyclohexylcatecholborane

cyclohexylboronic acid trimethylene glycol ester

isopropylboronic acid diethyl ester

B-isopropylcatecholborane

isopropylboronic acid pinacol ester

Examples of above-described boranes are:

B-n-butyl-9-borabicyclo[3.3.1]nonane=B-n-butyl-9-BBN

B-isoamyl-9-BBN

B-(hex-1-en-1-yl)-9-BBN

B-vinyl-9-BBN

B-cyclohexyl-9-BBN

B-(2-trimethylsilylethen-1-yl)-9-BBN

B-phenyl-9-BBN

B-(1-naphthyl)-9-BBN

B-(2-naphthyl)-9-BBN

B-(3,5-bis(trifluoromethyl)phenyl)-9-BBN

B-(2-phenylethyn-1-yl)-9-BBN

B-(2-phenylethen-1-yl)-9-BBN

B-benzyl-9-BBN

B-allyl-9-BBN

ethyldisiamylborane

n-butyldisiamylborane

amyldisiamylborane

cyclohexyldisiamylborane

vinyldisiamylborane

hex-1-en-1-yldisiamylborane

2-phenylethen-1-yldisiamylborane

2-trimethylsilylethen-1-yldisiamylborane

phenyldisiamylborane

naphthyldisiamylborane

benzyldisiamylborane

2-trimethylsilylethyn-1-yldisiamylborane

tributylborane

cyclohexyldibutylborane

vinyldibutylborane

hex-1-en-1-yldibutylborane

2-phenylethen-1-yldibutylborane

2-trimethylsilylethen-1-yldibutylborane

phenyldibutylborane

naphthyldibutylborane

benzyldibutylborane

2-trimethylsilylethyn-1-yldibutylborane

ethyldicyclohexylborane

n-butyldicyclohexylborane

amyldicyclohexylborane

vinyldicyclohexylborane

hex-1-en-1-yldicyclohexylborane

2-phenylethen-1-yldicyclohexylborane

2-trimethylsilylethen-1-yldicyclohexylborane

phenyldicyclohexylborane

naphthyldicyclohexylborane

benzyldicyclohexylborane

2-trimethylsilylethyn-1-yldicyclohexylborane

di-n-butylthexylborane

divinylthexylborane

dihex-1-en-1-ylthexylborane

diphenylthexylborane

dinaphthylthexylborane

bis-(2-trimethylsilylethen-1-yl)thexylborane

n-butyldibromoborane

n-butyldichloroborane

amyldibromoborane

cyclohexyldibromoborane

vinyldibromoborane

vinyldichloroborane

hex-1-en-1-yldibromoborane

2-phenylethen-1-yldibromoborane

2-phenylethen-1-yldichloroborane

2-trimethylsilylethen-1-yldifluoroborane

phenyldibromoborane

phenyldichloroborane

naphthyldibromoborane

benzyldibromoborane

2-trimethylsilylethyn-1-yldibromoborane

tert-butylethynyldifluoroborane

butyldiisopinocamphenylborane

vinyldiisopinocamphenylborane

hex-1-en-1-yldiisopinocamphenylborane

phenyldiisopinocamphenylborane

naphthyldiisopinocamphenylborane

2-trimethylsilylethen-1-yldiisopinocamphenylborane

Examples of above-described stannanes and distannanes are:

phenyltrimethylstannane

phenyltributylstannane

tetraphenylstannane

p-tolyltrimethylstannane

m-tolyltributylstannane

o-tolyltrimethylstannane

2,3-dimethylphenyltrimethylstannane

2,4-dimethylphenyltributylstannane

2,6-dimethylphenyltrimethylstannane

3,5-dimethylphenyltrimethylstannane

mesityltrimethylstannane

tetramethylphenyltrimethylstannane

butylphenyltrimethylstannane

tert-butylphenyltributylstannane

isopropylphenyltrimethylstannane

cyclohexylphenyltrimethylstannane

4-(hex-5-en-1-yl)phenyltrimethylstannane

triisopropylsilylphenyltrimethylstannane

p-methoxyphenyltrimethylstannane

m-methoxyphenyltributylstannane

o-methoxyphenyltrimethylstannane

2,4-dimethoxyphenyltrimethylstannane

2,5-dimethoxyphenyltrimethylstannane

3,5-dimethoxyphenyltributylstannane

2,3,4-trimethoxyphenyltrimethylstannane

2,4,6-trimethoxyphenyltrimethylstannane

3,4,5-trimethoxyphenyltributylstannane

p-phenoxyphenyltrimethylstannane

p-ethoxyphenyltrimethylstannane

2-(3′-phenyltrimethylstannane)-1,3-dioxolane

3,4-(methylenedioxy)phenyltrimethylstannane

3,4-(isopropylidenedioxy)phenyltrimethylstannane

p-thioanisyltributylstannane

m-thoianisyltrimethylstannane

o-thioanisyltrimethylstannane

p-nitrophenyltrimethylstannane

o-nitrophenyltributylstannane

m-nitrophenyltrimethylstannane

3-nitro-4-methylphenyltrimethylstannane

3-nitro-4-bromophenyltrimethylstannane

4-(methoxycarbonyl)phenyltributylstannane

3-(methoxycarbonyl)phenyltrimethylstannane

2-(methoxycarbonyl)phenyltrimethylstannane

4-carboxylphenyltrimethylstannane

3-carboxylphenyltributylstannane

2-carboxylphenyltrimethylstannane

formylphenyltrimethylstannane

acetylphenyltrimethylstannane

pivaloylphenyltrimethylstannane

o-fluorophenyltrimethylstannane

m-fluorophenyltrimethylstannane

p-fluorophenyltributylstannane

2,3-difluorophenyltrimethylstannane

2,4-difluorophenyltrimethylstannane

3,5-difluorophenyltriethylstannane

2,3,4-trifluorophenyltrimethylstannane

2,4,6-trifluorophenyltrimethylstannane

tetrafluorophenyltriethylstannane

pentafluorophenyltrimethylstannane

o-chlorophenyltrimethylstannane

m-chlorophenyltributylstannane

p-chlorophenyltrimethylstannane

3,5-dichlorophenyltrimethylstannane

2,4,6-trichlorophenyltrimethylstannane

p-bromophenyltrimethylstannane

p-trifluoromethylphenyltrimethylstannane

m-trifluoromethyltributylstannane

o-trifluoromethyltrimethylstannane

2,6-bis(trifluoromethyl)phenyltrimethylstannane

3,5-bis(trifluoromethyl)phenyltributylstannane

p-trifluoromethyltetrafluorophenyltrimethylstannane

trifluoromethoxyphenyltrimethylstannane

o-cyanophenyltrimethylstannane

m-cyanophenyltributylstannane

p-cyanophenyltrimethylstannane

tetrafluorocyanophenyltrimethylstannane

m-aminophenyltrimethylstannane

p-aminophenyltrimethylstannane

tetrafluoro-4-aminophenyltrimethylstannane

3-amino-4-methylphenyltrimethylstannane

p-dimethylaminophenyltrimethylstannane

m-dimethylaminophenyltriethylstannane

o-dimethylaminophenyltrimethylstannane

hydrazylphenyltrimethylstannane

p-hydroxyphenyltrimethylstannane

m-hydroxyphenyltributylstannane

o-hydroxyphenyltrimethylstannane

3-hydroxy-4-phenyltrimethylstannane

2,4-dihydroxyphenyltrimethylstannane

3,5-dihydroxyphenyltrimethylstannane

1-naphthyltrimethylstannane

1-naphthyltributylstannane

2-naphthyltrimethylstannane

2-methyl-1-naphthyltrimethylstannane

4-methyl-1-naphthyltrimethylstannane

4-methoxy-1-naphthyltrimethylstannane

6-methoxy-2-naphthyltrimethylstannane

2-biphenyltrimethylstannane

3-biphenyltrimethylstannane

4-biphenyltrimethylstannane

3,5-diphenylphenyltrimethylstannane

p-styryltrimethylstannane

m-styryltrimethylstannane

o-styryltrimethylstannane

9-anthracenetrimethylstannane

9-phenanthrenetrimethylstannane

2-furantrimethylstannane

3-furantrimethylstannane

benzofurantrimethylstannane

2-thiophenetrimethylstannane

3-thiophenetrimethylstannane

benzothiophenetrimethylstannane

N-methyl-2-pyrroletrimethylstannane

N-methyl-3-pyrroletrimethylstannane

thiazoletributylstannane

N-methylimidazoletrimethylstannane

N-methylbenzoimidazoletrimethylstannane

oxazoletributylstannane

benzothiazoletrimethylstannane

N-methyltriazoletributylstannane

2-pyridinetrimethylstannane

3-pyridinetrimethylstannane

4-pyridinetrimethylstannane

pyrimidinetrimethylstannane

2-quinolinetrimethylstannane

3-quinolinetrimethylstannane

4-isoquinolinetrimethylstannane

tetrafluoropyridinetrimethylstannane

vinyltrimethylstannane

2-trimethylsilylethene-1-tributylstannane

but-2-en-2-yltrimethylstannane

methyl 3-tributylstannyl acrylate

hexenyltrimethylstannane

cyclohexenyltrimethylstannane

2-phenylethenyltrimethylstannane

6-methoxyhex-1-ene-1-trimethylstannane

allyltrimethylstannane

benzyltrimethylstannane

p-methoxybenzyltrimethylstannane

ethynyltrimethylstannane

2-trimethylsilylethynyltrimethylstannane

2-phenylethynyltrimethylstannane

hex-1-ynyl-1-trimethylstannane

tert-butylacetylenetrimethylstannane

n-butyltrimethylstannane

cyclohexyltrimethylstannane

isopropyltrimethylstannane

hexamethyldistannane

hexaethyldistannane

hexabutyldistannane

hexaphenyldistannane

Examples of the above-described alkenes and alkynes are:

ethylene, styrene, α-methylstyrene, p-methylstyrene,2,4,6-trimethylstyrene, p-methoxystyrene, p-vinylstyrene,p-dimethylaminostyrene, p-chlorostyrene, p-aminostyrene,vinylnaphthalene, p-hydroxystyrene,

methyl acrylate, ethyl acrylate, butyl acrylate, octadecyl acrylate,t-butyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl acrylate,acrylamide, N,N-dimethylacrylamide, methyl methacrylate, ethylmethacrylate, butyl methacrylate, octadecyl methacrylate, t-butylmethacrylate, dimethylaminoethyl methacrylate, hydroxyethylmethacrylate, N,N-diethylmethacrylamide

acrylonitrile, methacrylonitrile vinylpyridines, butadiene, isoprene,phenylbutadiene, cyclohexene, cyclopentene,

methyl vinyl ketone, cyclohexenone, cyclopentenone, acrolein, acetylene,propyne, hexyne, phenylacetylene, t-butylacetylene,trimethylsilylacetylene, propargyl alcohol, methyl propynoate, propargylaldehyde, vinylacetylene, dihydrofuran, dihydropyran.

Examples of above-described silicon compounds are:

phenyltrimethylsilane

phenyltrifluorosilane

naphthyltrimethylsilane

naphthyltrifluorosilane

2-pyridyltrimethylsilane

p-methoxyphenyltriethylsilane

trifluoromethylphenyltrimethylsilane

vinyltrifluorosilane

vinyltrimethylsilane

hex-1-en-1-yltrimethylsilane

ethynyltrimethylsilane

ethynyltrichlorosilane

tert-butylethynyltrifluorosilane

Examples of above-described phosphorus compounds are:

diphenylphosphine

di(o-tolyl)phosphine

di(bis(trifluoromethyl)phenylphosphine)

trimethylstannyldi(p-methoxyphenyl)phosphine

trimethylsilyldiphenylphosphine

trimethylstannyldiphenylphosphine

dibutylphosphine

dimethylphosphine

triethylsilyldimethylphosphine

dicyclohexylphosphine

trimethylsilyldicyclohexylphosphine

trimethylstannylcyclohexylbutylphosphine

The process of the present invention for preparing indanones of theformula II or IIa can be carried out, for example, by reacting theindanones of the formula I or Ia with the above-described couplingcomponents such as boron-, carbon-, tin-, silicon- orphosphorus-containing compounds in a solvent, eg. a nonpolar, polaraprotic or polar protic solvent or any mixtures of components of thesesolvent classes.

Solvents which can be used are, for example, hydrocarbons, halogenatedhydrocarbons, ethers, polyethers, ketones, esters, amides, amines,ureas, sulfoxides, sulfones, phosphoramides, alcohols, polyalcohols,water and mixtures of these.

Preferred solvents are aromatics such as benzene, toluene, xylene,mesitylene, ethylbenzene, ethers such as diethyl ether, MTBE, THF,dioxane, anisole, di-n-butyl ether, DME, diglyme, triglyme, acetone,ethyl methyl ketone, isobutyl methyl ketone, ethyl acetate, DMF,dimethylacetamide, NMP, HMPA, acetonitrile, triethylamine, water,methanol, ethanol, isopropanol, isobutanol, ethylene glycol, diethyleneglycol, glycerol, triethylene glycol and mixtures of these.

Particular preference is given to toluene, xylene, diethyl ether, MTBE,THF, DME, diglyme, acetone, DMF, NMP, water, ethylene glycol andmixtures of these.

The process of the present invention can be carried out, if desired, inthe presence of a catalyst and, if desired, in the presence of a base, asalt-like additive or a phase transfer catalyst.

The catalysts which can be used in the process of the present inventioncomprise transition metal components such as transition metals ortransition metal compounds and, if desired, cocatalyst components whichcan act as ligands.

As transition metal components, preference is given to using transitionmetals of groups 6 to 12 of the Periodic Table of the Elements orcompounds of these transition metals.

Particularly preferred transition metal components are transition metalsof groups 8 to 10 of the Periodic Table of the Elements.

Preferred transition metal components are nickel, palladium and platinumand also compounds of these transition metals, in particular nickel andpalladium and also their compounds (J. Tsuji, Palladium-Reagents andCatalysts, Wiley 1995; M. Beller et al., Angew. Chem., 107, 1995, pp.1992-1993), which can, if desired, be used in the presence of one ormore cocatalysts.

Illustrative examples of catalysts, which, however, do not restrict thescope of the invention, are Ni(CO₄), NiCl₂(PPh₃)₂, NiCl₂(PBu₃)₂,Ni(PF₃)₄, Ni(COD)₂, Ni(PPh₃)₄, Ni(acac)₂, Ni(dppe)Cl₂, Ni(dppp)Cl₂,Ni(dppf)Cl₂, NiCl₂(PMe₃)₂, Pd(OAc)₂/PPh₃, Pd(OAc)₂/P(MeOPh)₃,Pd(OAc)₂/PBu₃, Pd(OAc)₂/AsPh₃, Pd(OAc)₂/SbPh₃, Pd(OAC)₂/dppe,Pd(OAC)₂/dppp, Pd(OAc)₂/dppf, Pd(OAc)₂/P(o-tolyl)₃,Pd(OAC)₂/tris(m-PhSO₃Na)phosphine, Pd(PPh₃)₄, Pd₂(dba)₃*CHCl₃,PdCl₂/PPh₃, PdCl₂/P(o-tolyl)₃, PdCl₂(PPh₃)₂, PdCl₂(MeCN)₂, PdCl₂(PhCN)₂,Pd(acac)₂, [(allyl)PdCl]₂, PdCl₂(dppp), PdCl₂(dppe), PdCl₂(COD),PdCl₂(dppf), Pd on carbon/PPh₃, Pd(OAc)₂/P(OMe)₃ and mononuclear andpolynuclear palladacycles.

Very particularly preferred catalysts are NiCl₂(PPh₃)₂, Ni(dppe)Cl₂,Ni(dppp)Cl₂, Ni(dppf)Cl₂, Pd(OAc)₂/PPh₃, Pd(OAC)₂/P(o-tolyl)₃,Pd(PPh₃)₄, PdCl₂(PPh₃)₂, PdCl₂/PPh₃, PdCl₂(dppp), PdCl₂(dppe),PdCl₂(dppf), Pd(OAc)₂/tris(m-PhSO₃Na)phosphine, and

The amount of catalyst used is generally from 100 mol % to 10⁻⁶ mol %,preferably from 10 mol % to 10⁻⁵ mol %, particularly preferably from 5mol % to 10⁻⁴ mol %, in each case based on the indanone of the formula Ior Ia.

If desired, the process of the present invention is carried out in thepresence of bases and/or phase transfer catalysts.

Illustrative examples of bases, which do not, however, restrict thescope of the invention, are hydroxides, alkoxides, carboxylates,carbonates and hydrogen carbonates, oxides, fluorides, phosphates andamines.

Preferred bases are Li₂CO₃, Na₂CO₃, NaHCO₃, K₂CO₃, Cs₂CO₃, LiOH, NaOH,KOH, CsOH, NaOMe, KO^(t)Bu, K₃PO₄, LiF, NaF, KF, CsF, NaOAc, KOAc,Ca(OAc)₂, K(t-BuCO₂), CaO, BaO, Ca(OH)₂, Ba(OH)₂, MgCO₃, CaCO₃, BaCO₃,TlOH, Tl₂CO₃, Ag₂O, ZnCO₃, Bu₄NF, [(Et₂N)₃S]Me₃SiF₂, DBU or amines suchas triethylamine, diisopropylethylamine, dicyclohexylethylamine ordimethylaniline.

Phase transfer catalysts which can be used are ammonium or phosphoniumsalts and also crown ethers. Illustrative examples of phase transfercatalysts, which do not, however, restrict the scope of the inventionare Bu₄NCl, Bu₄NBr, Bu₄NI, Bu₄NHSO₄, Et₃BnNBr, Me₃BnNCl, aliquot,Ph₄PBr, Ph₄PCl, 18-crown-6, 15-crown-5, 12-crown-4, dibenzo-18-crown-6.

If desired, the reaction can be carried out in the presence of one ormore salt-like additives. Illustrative examples of salt-like additives,which do not, however, restrict the scope of the invention, are LiCl,LiBr, LiF, Li, LiBF₄, LiPF₆, LiClO₄, LiCF₃CO₂, lithium triflate, LiNTf₂,AgNO₃, AgBF₄, AgCF₃CO₂, silver triflate, AgPF₆, CuCl, CuBr, CuJ, CuCN,Li₂Cu(CN)Cl₂, ZnCl₂, ZnBr₂, ZnI₂, zinc triflate and Zn(CF₃CO₂)₂.

The process of the present invention is generally carried out at from−100° C. to +600° C., preferably from −78° C. to +350° C., particularlypreferably at from 0° C. to 180° C.

The reaction generally takes place at a pressure of from 10 mbar to 1000bar, preferably from 0.5 bar to 100 bar.

The reaction can be carried out in a single-phase system or in amultiphase system.

The concentration of indanone of the formula I or Ia in the reactionmixture is generally in the range from 0.0001 mol/l to 8 mol/l,preferably from 0.01 mol/l to 3 mol/l, particularly preferably from 0.1mol/l to 2 mol/l.

The molar ratio of coupling component to indanone of the formula I or Iais generally from 0.1 to 10, preferably from 0.5 to 3.

The molar ratio of base to indanone of the formula I or Ia is generallyfrom 0 to 50.

The molar ratio of phase transfer catalyst to indanone of the formula Ior Ia is generally from 0 to 2, preferably from 0 to 0.1.

The molar ratio of salt-like additives to indanone of the formula I orIa is generally from 0 to 10.

The time of the reaction of indanones of the formula I or Ia withabove-described coupling components to give indanones of the formula IIor IIa is generally from 5 minutes to 1 week, preferably from 15 minutesto 48 hours.

The reaction of an indanone of the formula I or Ia with a boronic acidis preferably carried out under conditions in which the transition metalcomponent used is a compound of a transition metal of groups 8 to 10 ofthe Periodic Table of the Elements, a base such as an alkoxide,hydroxide, carbonate, carboxylate, hydrogencarbonate, oxide, fluoride,phosphate or amine is used and a solvent such as a hydrocarbon, ether,polyether, alcohol, polyalcohol or water or any mixture of these is usedand the reaction temperature is from −100° to 500° C.

Particular preference is given to conditions in which the transitionmetal component used is a compound of the transition metals Ni, Pd orPt, the base used is an alkoxide, hydroxide, hydrogencarbonate,carbonate, carboxylate or phosphate, the solvent used is an aromatichydrocarbon, ether, polyether, alcohol, polyalcohol or water or anymixture of these and the reaction temperature is from −78 to 300° C.

Very particular preference is given to conditions in which thetransition metal component used is a palladium compound, the base is analkali metal or alkaline earth metal alkoxide, hydroxide, carbonate,carboxylate or orthophosphate, the solvent is toluene, xylene,mesitylene, ethylbenzene, THF, dioxane, DME, diglyme, butanol, ethyleneglycol, glycerol or water or any mixture of these and the reactiontemperature is from −30° to 200° C.

Extraordinary preference is given to conditions in which the transitionmetal compound is a palladium compound, the base is an alkali metal oralkaline earth metal carbonate, hydroxide or orthophosphate, the solventis toluene, xylene, THF, DME, diglyme, ethylene glycol or water or anymixture of these and the reaction temperature is from 0° C. to 160° C.

Illustrative examples of reaction conditions in the reaction of anindanone of the formula I or Ia with a boronic acid, which do not,however, restrict the scope of the invention, are:

X (in formula I or Ia)=Br; catalyst: 0.01-5 mol % of Pd(P(Ph₃)₄); base:aqueous sodium carbonate solution; solvent: toluene; reactiontemperature: reflux; reaction time: 1-24 h.

X (in formula I or Ia)=Cl; catalyst: 0.01-15 mol % of NiCl₂(dppf); base:K₃PO₄; solvent: dioxane; reaction temperature: 80° C.; reaction time:1-24 h.

X (in formula I or Ia)=Br; catalyst: 0.01-5 mol % of Pd(OAc)₂/PPh₃;base: aqueous potassium carbonate solution; solvent: xylene; reactiontemperature: reflux; reaction time: 1-24 h.

X (in formula I or Ia)=Cl or Br; catalyst: 0.01-5 mol % ofPd(OAc)₂/P(m-HSO₃-Ph)₃; base: aqueous sodium carbonate solution;solvent: xylene/ethylene glycol; reaction temperature: reflux; reactiontime: 1-24 h.

X (in formula I or Ia)=I or trifluoromethanesulfonate; catalyst: 0.01-1mol % of PdCl₂(NC-Ph)₂; base: sodium carbonate; solvent: DME; additive:5 mol % of tetrabutylammonium bromide; reaction temperature: reflux;reaction time: 1-24 h.

X (in formula I or Ia)=Br; catalyst: 0.01-5 mol % of Pd(OAc)₂/P(o-tol)₃;base: triethylamine; solvent: dimethylformamide (DMF); reactiontemperature: 100° C.; reaction time: 1-24 h.

Preference is given to carrying out the reaction of an indanone of theformula I or Ia with a stannane to give indanones of the formula II orIIa, where

R³ is preferably an aryl, heteroaryl or alkenyl group, the transitionmetal compound is a compound of a transition metal of groups 8-10 of thePeriodic Table of the Elements,

the solvent is a hydrocarbon, ether, polyether, amide or nitrile,

the additive is a lithium salt, a zinc salt, a copper salt, a silversalt or a fluoride salt and

the reaction temperature is from −78° C. to 300° C. and the reactiontime is from 5 minutes to 1 week.

In the reaction with a stannane, particular preference is given toconditions in which

R³ is preferably an aryl, heteroaryl (with the heteroatoms N, O and S)or alkenyl group, and in which the transition metal component is apalladium compound,

the solvent is an aromatic hydrocarbon, ether, THF, dioxane, DME, DMF,HMPA, NMP or acetonitrile,

the additive is a lithium or copper(I) salt and

the reaction temperature is from −30 to 200° C. and the reaction time isfrom 10 minutes to 48 hours.

Illustrative examples of reaction conditions in the reaction of anindanone of the formula I or Ia with a stannane, which do not, however,restrict the scope of the invention, are:

X (in formula I or Ia)=I; catalyst: 0.1-5 mol % of PdCl₂(PPh₃)₂;solvent: DME; additive: lithium chloride; temperature: 85° C.; reactiontime: 12-24 h.

X (in formula I or Ia)=Br; catalyst: 0.5-10 mol % ofPd(OAc)₂/P(o-tolyl)₃; solvent: xylene; additive: CuI; temperature: 135°C.; reaction time: 3-6 h.

The reaction of an indanone of the formula I and Ia with an olefin ispreferably carried out under conditions in which the transition metalcomponent is a compound of a transition metal of groups 8-10 of thePeriod Table of the Elements,

the base is an amine or carboxylate,

the solvent is an amide, amine, urea, nitrile, alcohol or water and thereaction temperature is from −78 to 250° C.

Particular preference is given to conditions in which the transitionmetal component is a palladium compound,

the base is a tertiary amine, carboxylate or DBU,

the solvent is an amide, nitrile or alcohol and the reaction temperatureis from 0 to 200° C.

Illustrative examples of reaction conditions in the reaction of anindanone of the formula I or Ia with an olefin, which do not, however,restrict the scope of the invention, are:

X (in formula I or Ia)=Br; olefin: butyl acrylate; catalyst: 0.01-5 mol% of Pd(OAc)₂/PPh₃; base: triethylamine; solvent: dimethylformamide;temperature 130° C.

X (in formula I or Ia)=trifluoromethanesulfonate; olefin: methylmethacrylate; catalyst: 0.01-5 mol % of Pd/C/PPh₃; base:diisopropylethylamine; solvent: dimethylacetamide; temperature: 130° C.

X (in formula I or Ia)=Cl; olefin: acrylonitrile; catalyst: 0.01-1 mol %of [(o-tolyl)₂P-(o-benzyl)Pd]₂(OAc)₂; base: sodium acetate; solvent:acetonitrile; temperature: 100° C.

The present invention also provides substituted indanones of the formulaIII,

where

R^(1′) is a C₁-C₄₀-hydrocarbon group which is bound via a carbon atomand may bear one or more identical or different heteroatom-containingradicals, except for nitrogen-containing radicals, as substituents, eg.a linear, branched or cyclic C₁-C₂₀-alkyl group which may bear one ormore identical or different halogen, OH, OR², SR², PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents, a C₆-C₂₂-aryl group which may bear one or moreidentical or different halogen, OH, OR², SR², PR² ₂—, —SiR² ₃ or —OSiR²₃ substituents, a C₇-C₂₀-alkylaryl group or a C₇-C₂₀-arylalkyl group,where the alkyl part may bear one or more identical or differenthalogen, OH, OR², SR², PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents and thearyl part may bear one or more identical or different halogen, OH, OR²,SR², PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₂-C₁₂-alkenyl groupwhich may bear one or more identical or different halogen, OH, OR², SR²,PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₂-C₂₀-alkynyl group whichmay bear one or more identical or different halogen, OH, OR², SR², PR²₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₈-C₁₂-arylalkenyl group, wherethe alkenyl part may bear one or more identical or different halogen,OH, OR², SR², PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents and the aryl partmay bear one or more identical or different halogen, OH, OR², SR², PR²₂—, —SiR² ₃ or —OSiR² ₃ substituents, or

R^(1′) is an OR², SR², NR² ₂, PR² ₂, SiR² ₃ or OSiR² ₃ group, where R²are identical or different and are each a C₁-C₂₀-hydrocarbon group suchas a C₁-C₁₀-alkyl or C₆-C₁₄-aryl group which may each bear one or moreidentical or different halogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents, or two radicals R² may be joined to form a ringsystem or

R^(1′) is a C₁-C₂₀-, preferably C₂-C₂₀-heterocyclic group which is boundvia a carbon atom and may in turn bear C₁-C₂₀-radicals or heteroatoms assubstituents,

X′ is a leaving group, preferably a diazonium group, a halogen atom suchas chlorine, bromine or iodine, or C₁-C₄₀-alkyl-sulfonate,C₁-C₄₀-haloalkylsulfonate, C₆-C₄₀-arylsulfonate,C₆-C₄₀-haloarylsulfonate, C₇-C₄₀-arylalkylsulfonate,C₇-C₄₀-haloarylalkylsulfonate, C₁-C₄₀-alkylcarboxylate,C₁-C₄₀-haloalkylcarboxylate, C₆-C₄₀-arylcarboxylate,C₆-C₄₀-haloarylcarboxylate, C₇-C₄₀-arylalkylcarboxylate,C₇-C₄₀-haloarylalkylcarboxylate, formate, C₁-C₄₀-alkyl carbonate,C₁-C₄₀-haloalkyl carbonate, C₆-C₄₀-aryl carbonate, C₆-C₄₀-haloarylcarbonate, C₇-C₄₀-arylalkyl carbonate, C₇-C₄₀-haloarylalkyl carbonate,C₁-C₄₀-alkyl phosphonate, C₁-C₄₀-haloalkyl phosphonate, C₆-C₄₀-arylphosphonate, C₆-C₄₀-haloaryl phosphonate, C₇-C₄₀-arylalkyl phosphonateor C₇-C₄₀-haloarylalkyl phosphonate,

Y⁷ and Y⁸ are identical or different and are each a hydrogen atom or areas defined for X′ or are a C₂-C₄₀-hydrocarbon group which is bound via acarbon atom and may bear one or more identical or differentheteroatom-containing radicals as substituents, eg. a linear, branchedor cyclic C₂-C₂₀-alkyl group which may bear one or more identical ordifferent halogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents, a C₆-C₂₂-aryl group which may bear one or more identicalor different halogen, OR², SR², NR² ₂—, NH₂, —N₂H₃, NO₂, CN, CO₂R², CHO,COR², PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₇-C₁₅-alkylaryl groupor C₇-C₁₅-arylalkyl group, where the alkyl part may bear one or moreidentical or different halogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents and the aryl part may bear one or more identicalor different halogen, OR², SR², NR² ₂—, NH₂, —N₂H₃, NO₂, CN, CO₂R², CHO,PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₂-C₁₀-alkenyl group whichmay bear one or more identical or different halogen, OH, OR², SR², NR²₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₂-C₁₀-alkynyl groupwhich may bear one or more identical or different halogen, OH, OR², SR²,NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₈-C₁₂-arylalkenylgroup which may bear one or more identical or different halogen, OH,OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, or

Y⁷ and Y⁸ are each a halogen atom, a NR² ₂, PR² ₂, B(OR²)₂, SiR² ₃ orSnR² ₃ group, where R² are identical or different and are each aC₁-C₂₀-hydrocarbon group, eg. a C₁-C₁₀-alkyl group or C₆-C₁₄-aryl groupwhich may bear one or more identical or different halogen, OH, OR², SR²,NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, or two radicals R² maybe joined to form a ring system, or

Y⁷ and Y⁸ are each a C₁-C₂₀-heterocyclic group which is bound via acarbon atom and may in turn bear C₁-C₂₀-radicals or heteroatoms assubstituents, and

in formula III, at least one of the radicals Y⁷ and Y⁸, preferably Y⁷,is a hydrogen atom and Y⁹ is a hydrogen atom.

Particular preference is given to indanones of the formula III in which

X′ is chlorine, bromine, iodine, triflate, nonaflate, mesylate,ethylsulfonate, benzenesulfonate, tosylate,triisopropylbenzenesulfonate, formate, acetate, trifluoroacetate,nitrobenzoate, halogenated arylcarboxylates, in particular fluorinatedbenzoate, methyl carbonate, ethyl carbonate, benzyl carbonate,tert-butyl carbonate, dimethyl phosphonate, diethyl phosphonate,diphenyl phosphonate or diazonium,

R^(1′) is a linear, branched or cyclic C₁-C₈-alkyl group which may bearone or more identical or different fluorine, chlorine, OR^(Z), —SiR² ₃or —OSiR² ₃ substituents, a C₆-C₁₀-aryl group which may bear one or moreidentical or different fluorine, chlorine, OR², SR², —SiR² ₃ or —OSiR² ₃substituents, a C₇-C₁₂-alkylaryl or arylalkyl group, where the alkylpart may bear one or more identical or different fluorine, chlorine,OR², SR², —SiR² ₃ or —OSiR² ₃ substituents and the aryl part may bearone or more identical or different fluorine, chlorine, OR², SR², —SiR² ₃or —OSiR² ₃ substituents, a C₂-C₈-alkenyl group, C₂-C₈-alkynyl group, aC₈-C₁₂-arylalkenyl group, an OR², —SiR² ₃ or —OSiR² ₃ group, where R²are identical or different and are each a C₁-C₄-alkyl or C₆-C₁₀-arylgroup, or

R^(1′) is a C₁-C₂₀-heterocyclic group, where preferred heteroatoms areoxygen and sulfur, which may in turn bear C₁-C₂₀-hydrocarbon radicals assubstituents.

Very particular preference is given to indanones of the formula III inwhich

X′ is chlorine, bromine, iodine, triflate or mesylate,

R^(1′) is a linear, branched or cyclic C₁-C₈-alkyl group which may bearone or more fluorine substituents, a C₆-aryl group which may bear one ormore identical or different fluorine, chlorine or OR² substituents, aC₇-C₁₀-alkylaryl or arylalkyl group, where the alkyl part may bear oneor more identical or different fluorine, chlorine or OR² substituentsand the aryl part may bear one or more identical or different fluorine,chlorine or OR² substituents, a C₂-C₈-alkenyl group or C₂-C₈-alkynylgroup which may each bear one or more identical or different fluorine orOR² substituents, a C₈-C₁₂-arylalkenyl group, an OR², SiR² ₃ or —OSiR² ₃group, where R² are identical or different and are each a C₁-C₄-alkyl orC₆-aryl group, or R^(1′) is a C₁-C₁₆-heterocyclic group, where preferredheteroatoms are oxygen and sulfur, and Y⁷ is a hydrogen atom and Y⁸ is ahydrogen atom or is as defined for X′ or Y⁸ is a linear, branched orcyclic C₂-C₆-alkyl group which may bear one or more fluorinesubstituents, a C₆-C₁₀-aryl group which may bear one or more fluorinesubstituents, a C₇-C₁₂-alkylaryl group or C₇-C₁₂-arylalkyl group, wherethe alkyl part may bear one or more fluorine substituents and the arylpart may bear one or more fluorine substituents, a C₂-C₈-alkenyl group,a C₂-C₈-alkynyl group, a C₈-C₁₀-arylalkenyl group or

Y⁸ is a C₁-C₉-heterocyclic group which is bound via a carbon atom andmay in turn bear C₁-C₆-radicals or heteroatoms as substituents;preferably, Y⁸ is as defined for X′ or is a C₆-C₁₄-aryl group.

Extraordinary preference is given to indanones of the formula III inwhich

X′ is chlorine, bromine or triflate,

R^(1′) is a linear, branched or cyclic C₁-C₆-alkyl group, aC₇-C₁₀-alkylaryl or arylalkyl group, a C₂-C₆-alkenyl group orC₂-C₆-alkynyl group or a C₈-C₁₀-arylalkenyl group and

Y⁷, Y⁸ and Y⁹ are each a hydrogen atom.

Illustrative examples of indanones of the formula III, which do not,however, restrict the scope of the invention, are:

2-methyl-7-chloro-1-indanone

2-methyl-7-bromo-1-indanone

2-methyl-7-iodo-1-indanone

2-methyl-7-trifluoroacetoxy-1-indanone

2-methyl-7-trifluoromethanesulfonoxy-1-indanone

2-methyl-7-methanesulfonoxy-1-indanone

2-methyl-7-ethanesulfonoxy-1-indanone

2-methyl-7-(p-toluenesulfonoxy)-1-indanone

2-methyl-7-benzenesulfonoxy-1-indanone

2-methyl-7-(2,4,6-triisopropylbenzenesulfonoxy)-1-indanone

2-methyl-7-pentafluorobenzenesulfonoxy-1-indanone

2-methyl-7-nonafluorobutanesulfonoxy-1-indanone

2-methyl-7-acetoxy-1-indanone

2-methyl-7-formyloxy-1-indanone

2-methyl-7-pentafluorobenzoyloxy-1-indanone

2-methyl-7-(p-nitrobenzoyloxy)-1-indanone

2-methyl-7-methoxycarbonyloxy-1-indanone

2-methyl-7-tert-butyloxycarbonyloxy-1-indanone

2-methyl-7-ethoxycarbonyloxy-1-indanone

2-methyl-7-benzyloxycarbonyloxy-1-indanone

2-methyl-7-dimethylphosphonoxy-1-indanone

2-methyl-7-diethylphosphonoxy-1-indanone

2-methyl-7-diphenylphosphonoxy-1-indanone

2-methyl-7-diazonium-1-indanone chloride

2-methyl-7-diazonium-1-indanone tetrafluoroborate

2-methyl-7-diazonium-1-indanone sulfate

2-methyl-5-butyl-7-bromo-1-indanone

2-methyl-5-fluoro-7-bromo-1-indanone

2-methyl-5,7-dibromo-1-indanone

2-methyl-5,7-dichloro-1-indanone

2-methyl-6,7-dichloro-1-indanone

2-methyl-5-chloro-7-bromo-1-indanone

2,6-dimethyl-7-chloro-1-indanone

2-methyl-5-butyl-7-chloro-1-indanone

2-methyl-5-isopropyl-7-trifluoromethanesulfonoxy-1-indanone

2-methyl-5-tert-butyl-7-methanesulfonoxy-1-indanone

2-methyl-5-phenyl-7-bromo-1-indanone

2-methyl-5-(3,5-dimethoxyphenyl)-7-iodo-1-indanone

2-methyl-5-benzyl-7-chloro-1-indanone

2-methyl-5-vinyl-7-(p-toluenesulfonoxy)-1-indanone

2-methyl-6-bromo-7-trifluoroacetoxy-1-indanone

2-methyl-6-phenyl-7-bromo-1-indanone

2-trifluoromethyl-7-chloro-1-indanone

2-trifluoromethyl-7-bromo-1-indanone

2-trifluoromethyl-5-isobutyl-7-trifluoromethanesulfonoxy-1-indanone

2-ethyl-7-chloro-1-indanone

2-ethyl-7-bromo-1-indanone

2-ethyl-7-diazonium-1-indanone tetrafluoroborate

2-ethyl-7-methanesulfonoxy-1-indanone

2-ethyl-5-methyl-7-bromo-1-indanone

2-ethyl-7-diazonium-1-indanone tetrafluoroborate

2,6-diethyl-7-diazonium-1-indanone chloride

2-butyl-7-chloro-1-indanone

2-butyl-5-fluoro-7-chloro-1-indanone

2-n-propyl-7-chloro-1-indanone

2-n-propyl-7-bromo-1-indanone

2-butyl-5,7-dichloro-1-indanone

2-isopropyl-7-chloro-1-indanone

2-isopropyl-7-bromo-1-indanone

2-isopropyl-7-iodo-1-indanone

2-isopropyl-5-diphenylphosphino-7-nonafluorobutanesulfonoxy-1-indanone

2-phenyl-7-chloro-1-indanone

2-(2-pyridyl)-7-bromo-1-indanone

2-(2-furyl)-7-iodo-1-indanone

2-cyclohexyl-7-chloro-1-indanone

2-cyclohexyl-7-bromo-1-indanone

2-cyclohexyl-7-trifluoromethanesulfonoxy-1-indanone

2-isobutyl-7-chloro-1-indanone

2-isobutyl-7-bromo-1-indanone

2-tert-butyl-7-chloro-1-indanone

2-tert-butyl-7-iodo-1-indanone

2-benzyl-7-chloro-1-indanone

2-allyl-7-chloro-1-indanone

2-vinyl-7-trifluoromethanesulfonoxy-1-indanone

2-(2-trimethylsilylethyn-1-yl)-6-benzyl-7-chloroindanone

2-(hex-1-ynyl)-7-trifluoromethanesulfonoxy-1-indanone

2-trimethylsilyl-7-bromo-1-indanone

2-trimethylsilyloxy-7-bromo-1-indanone

2-dimethylamino-7-trifluoromethanesulfonoxy-1-indanone

2-N-pyrrolidino-7-chloro-1-indanone

2-diphenylphosphino-5-isopropyl-7-bromo-1-indanone

2-methoxy-6-allyl-7-chloro-1-indanone

2,6-dimethoxy-7-bromo-1-indanone

2-phenoxy-5-dimethylamino-7-trifluoromethanesulfonoxy-1-indanone

2-(2-methoxyethyl)-7-chloro-1-indanone

2-(3-chloropropyl)-7-chloro-1-indanone

The indanones of the formula I or Ia can be prepared by methods similarto those known from the literature (eg. U.S. Pat. No. 5,489,712; U.S.Pat. No. 4,070,539; S. J. deSolms et al., J. Med. Chem., 1978, 21, 437).To prepare indanones of the formula I, for example, an aryl alkyl ketoneof the formula (A) can be methylenated and subsequently subjected to aNazarov cyclization.

R¹, X, Y¹, Y² and Y³ in the formulae A, B and I are as defined above forformula I.

In the case of an aryl alkyl ketone, the methylene group can, forexample, be introduced by an aldol condensation with formaldehyde asmethylene source or by a Mannich reaction, in which, for example,N,N,N′,N′-tetramethyldiaminomethane, Eschenmoser's salt orurotropien/acetic anhydride can be used as methylene source. It isindicated in the literature (U.S. Pat. No. 5,489,712) that the aldolcondensation of formaldehyde, which is the most inexpensive methylenesource, and aryl alkyl ketones proceeds in poor yields and themanagement of the reaction is said to be complicated. M. M. Curzu et al.in Synthesis (1984) 339 state that in the aldol condensation offormaldehyde and certain aryl alkyl ketones, considerable amounts ofstarting material remain unreacted and undesirable by-products such asthe primary aldol product containing a hydroxymethyl group are presentin the end product.

It has surprisingly been found that the aldol condensation (ie. theintroduction of the methylene group) of aryl alkyl ketones proceedsvirtually quantitatively under basic conditions using formaldehyde, andthe primary aldol product containing a hydroxymethyl group cannot beobserved spectroscopically. Here, preferred aryl alkyl ketones of theformula A are those in which X is a halogen.

The aldol condensation is carried out using a formaldehyde source,preferably aqueous formalin solution, and a base, preferably an alkalimetal carbonate or alkaline earth metal carbonate or an alkali metalhydroxide or alkaline earth metal hydroxide, particularly preferably anaqueous sodium hydroxide solution, at 0-100° C., preferably 20-60° C.

The molar ratio of base to aryl alkyl ketone is in the range from 0.01to 5, preferably in the range from 0.1 to 2.

The molar ratio of formaldehyde to aryl alkyl ketone is in the rangefrom 0.5 to 1.5, preferably in the range from 0.9 to 1.2.

The concentration of the aryl alkyl ketone in the reaction mixture(total volume) is in the range from 0.01 to 6 mol/l, preferably from 0.1to 2 mol/l. The aryl alkyl ketone can be diluted with inert solventssuch as ethers, hydrocarbons or halogenated hydrocarbons. The reactioncan be carried out in a single-phase or multiphase system.

In the case of multiphase reaction mixtures, phase transfer catalystscan be added to accelerate the reaction.

The reaction time is usually from 15 minutes to 12 hours or longer.

The reaction can also be carried out in an inert gas atmosphere and thepressure in the reaction vessel can be either below or above atmosphericpressure.

The subsequent cyclization to form the indanone is carried out byliterature methods (J. H. Burckhalter, R. C. Fuson, J. Amer. Chem. Soc.,1948, 70, 4184; E. D. Thorsett, F. R. Stermitz, Synth. Commun., 1972, 2,375; Synth. Commun., A. Bhattacharya, B. Segmuller, A. Ybarra, 1996, 26,1775; U.S. Pat. No. 5,489,712). The cyclization is preferably carriedout under acid conditions. As cyclization reagent, it is possible to useacids such as protic acids (eg. sulfuric acid, polyphosphoric acid,methanesulfonic acid) or Lewis acids (eg. aluminum trichloride, borontrifluoride). The reaction product from the aldol condensation can bediluted with an inert solvent before addition to the cyclizationreagent, or can be added in undiluted form.

To prepare indanones of the formula I and Ia in which X is anoxygen-containing leaving group, for example a triflate group, thestarting materials used are preferably hydroxyindanones, some of whichare known from the literature (eg. Bringmann et al., Liebigs Ann. Chem.,1985, 2116-2125), and the hydroxy group is converted by literaturemethods into an oxygen-containing leaving group X, eg. triflate (eg.: P.J. Stang, Synthesis, 1982, 85; V. Percec, J. Org. Chem., 1995, 60, 176;Autorenkollektiv, Organikum, VEB Deutscher Verlag der Wissenschaften,1976).

Some of the aryl alkyl ketones are known from the literature or they caneasily be prepared by literature methods (eg.: R. C. Larock,Comprehensive Organic Transformations, VCH, 1989).

The invention further provides substituted indanones of the formula IV

R^(1″) is a C₁-C₄₀-group such as a C₁-C₄₀-hydrocarbon group which isbound via a carbon atom and may bear one or more identical or differentheteroatom-containing radicals as substituents, eg. a linear, branchedor cyclic C₁-C₂₀-alkyl group which may bear one or more identical ordifferent halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents, a C₆-C₂₂-aryl group which may bear one or more identicalor different halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents, a C₇-C₂₀-alkylaryl group or a C₇-C₂₀-arylalkyl group,where the alkyl part may bear one or more identical or differenthalogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituentsand the aryl part may bear one or more identical or different halogen,OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, aC₂-C₁₀-alkenyl group which may bear one or more identical or differenthalogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, aC₂-C₂₀-alkynyl group which may bear one or more identical or differenthalogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, aC₈-C₁₂-arylalkenyl group, where the alkenyl part may bear one or moreidentical or different halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents and the aryl part may bear one or more identicalor different halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents, or

R^(1″) is an OR², SR², NR² ₂, PR² ₂, SiR² ₃ or OSiR² ₃ group, where R²are identical or different and are each a C₁-C₂₀-hydrocarbon group suchas a C₁-C₁₀-alkyl or C₆-C₁₄-aryl group which may each bear one or moreidentical or different halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents, or two radicals R² may be joined to form a ringsystem, or

R^(1″) is a C₁-C₂₀-heterocyclic group which is bound via a carbon atomand may in turn bear C₁-C₂₀-radicals or heteroatoms as substituents,

R^(3′) is an unsaturated C₂-C₄₀-group such as an unsaturatedC₂-C₄₀-hydrocarbon group which is bound via a carbon atom and may bearone or more identical or different heteroatom-containing radicals assubstituents, eg. a C₆-C₂₂-aryl group which may bear one or moreidentical or different halogen, OR², SR²NR² ₂—, NH₂, —N₂H₃, NO₂, CN,CO₂R², CHO, COR², PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, aC₇-C₁₅-alkylaryl group or C₇-C₁₅-arylalkyl group, where the alkyl partmay bear one or more identical or different halogen, OH, OR², SR²NR² ₂—,PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents and the aryl part may bear oneor more identical or different halogen, OR², SR²NR² ₂—, NH₂, —N₂H₃, NO₂,CN, CO₂R², CHO, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, aC₂-C₁₀-alkenyl group which may bear one or more identical or differenthalogen, OH, OR², CO₂R², COR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents, a C₂-C₁₀-alkynyl group which may bear one or moreidentical or different halogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents, a C₈-C₁₂-arylalkenyl group, which may bear one ormore identical or different halogen, OH, OR², CO₂R², COR², SR², NR² ₂—,PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, or

R^(3′) is fluorine, a PR² ₂, B(OR²)₂, SiR₂ ³ or SnR² ₃ group, where R²are identical or different and are each a C₁-C₂₀-hydrocarbon group, eg.a C₁-C₁₀-alkyl group or C₆-C₁₄-aryl group which may each bear one ormore identical or different halogen, OH, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃or —OSiR² ₃ substituents, or two radicals R² may be joined to form aring system, or

R^(3′) is a C₁-C₂₀-heterocyclic group which is bound via a carbon atomand may in turn bear C₁-C₂₀-radicals or heteroatoms as substituents, and

Y¹⁰ and Y¹¹ are identical or different and are each a hydrogen atom orare as defined for R³ in formula II, ie.

are a C₁-C₄₀-hydrocarbon group which is bound via a carbon atom and maybear one or more identical or different heteroatom-containing radicalsas substituents, eg. a linear, branched or cyclic C₁-C₂₀-alkyl groupwhich may bear one or more identical or different halogen, OH, OR², SR²,NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₆-C₂₂-aryl groupwhich may bear one or more identical or different halogen, OR², SR²NR²₂—, NH₂, —N₂H₃, NO₂, CN, CO₂R², CHO, COR², PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents, a C₇-C₁₅-alkylaryl group or C₇-C₁₅-arylalkyl group, wherethe alkyl part may bear one or more identical or different halogen, OH,OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents and the arylpart may bear one or more identical or different halogen, OR², SR²NR²₂—, NH₂, —N₂H₃, NO₂, CN, CO₂R², CHO, PR² ₂—, —SiR² ₃ or —OSiR² ₃substituents, a C₂-C₁₀-alkenyl group which may bear one or moreidentical or different halogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents, a C₂-C₁₀-alkynyl group which may bear one or moreidentical or different halogen, OH, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents, a C₈-C₁₂-arylalkenyl group, which may bear one ormore identical or different halogen, OH, OR², CO₂R², COR², SR², NR² ₂—,PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, or

Y¹⁰ or Y¹¹ are a halogen atom, a PR² ₂, B(OR²)₂, SiR₂ ³ or SnR² ₃ group,where R² are identical or different and are each a C₁-C₂₀-hydrocarbongroup, eg. a C₁-C₁₀-alkyl group or C₆-C₁₄-aryl group which may each bearone or more identical or different halogen, OH, OR², SR²NR² ₂—, PR² ₂—,—SiR² ₃ or —OSiR² ₃ substituents, or two radicals R² may be joined toform a ring system, or

Y¹⁰ or Y¹¹ are each a C₁-C₂₀-heterocyclic group which is bound via acarbon atom and may in turn bear C₁-C₂₀-radicals or heteroatoms assubstituents;

in formula IV, at least one of the radicals Y¹⁰ and Y¹¹, preferably Y¹⁰, is a hydrogen atom and Y¹² is a hydrogen atom.

Preference is given to indanones of the formula IV in which

R^(1″) is a linear, branched or cyclic C₁-C₈-alkyl group which may bearone or more identical or different fluorine, chlorine, OR², PR² ₂—, NR²₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₆-C₁₀-aryl group which may bearone or more identical or different fluorine, chlorine, OR², SR², NR² ₂—,PR² ₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₇-C₁₂-alkylaryl orarylalkyl group, where the alkyl part may bear one or more identical ordifferent fluorine, chlorine, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents and the aryl part may bear one or more identicalor different fluorine, chlorine, OR², SR²NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents, a C₂-C₆-alkenyl group, C₂-C₆-alkynyl group, aC₈-C₁₂-arylalkenyl group, an OR², PR² ₂—, NR² ₂—, —SiR² ₃ or —OSiR² ₃group where R² are identical or different and are each a C₁-C₄-alkyl orC₆-C₁₀-aryl group, where the alkyl group may bear one or more identicalor different fluorine, chlorine, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents and the aryl group may bear 1-3 substituents suchas fluorine, chlorine, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or —OSiR² ₃₁ ora C₁-C₂₀-heterocyclic group, where preferred heteroatoms are oxygen,nitrogen, sulfur, phosphorus and silicon, which may in turn bear C₁-C₁₀radicals or heteroatoms as substituents, and

R^(3′) is an unsaturated C₂-C₂₀-group, a C₆-C₁₄-aryl group which mayeach bear one or more identical or different fluorine, chlorine, OR²,SR², NR₂, NH₂, —N₂H₃, NO₂, CN, CO₂R², COR², CHO, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents, a C₇-C₁₅-alkylaryl group or C₇-C₁₅-arylalkylgroup, where the alkyl part may bear one or more identical or differentfluorine, chlorine, OR², CO₂R², COR², NR² ₂— or —OSiR² ₃ substituentsand the aryl part may bear one or more identical or different fluorine,chlorine, OR², SR², NR² ₂—, NH₂, —N₂H₃, NO₂, CN, CO₂R², COR², CHO, PR²₂—, —SiR² ₃ or —OSiR² ₃ substituents, a C₂-C₁₀-alkenyl group which maybear one or more identical or different fluorine, chlorine, OR², CO₂R²,COR², NR² ₂— or —OSiR² ₃ substituents, a C₂-C₁₀-alkynyl group which maybear one or more identical or different fluorine, chlorine, OR², CO₂R²,CONR² ₂— or —OSiR² ₃ substituents, a C₈-C₁₂-arylalkenyl group which maybear one or more identical or different fluorine, chlorine, CO₂R², COR²,OR², NR₂ ²— or —OSiR² ₃ substituents, a PR² ₂, B(OR²)₂, SiR² ₃ or SnR² ₃group where R² are identical or different and are each a C₁-C₄-alkyl orC₆-C₁₀-aryl group, where the alkyl group may bear one or more identicalor different fluorine, chlorine, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents and the aryl group may bear one or more identicalor different fluorine, chlorine, OR², SR², NR² ₂—, PR² ₂—, —SiR² ₃ or—OSiR² ₃ substituents, and, in addition, two radicals R² may be joinedto one another to form a ring system, a C₂-C₂₀-heterocyclic group, wherepreferred heteroatoms are oxygen, nitrogen, sulfur, phosphorus andsilicon, which may in turn bear C₁-C₁₀ radicals or heteroatoms assubstituents.

Particular preference is given to indanones of the formula IV in which

R^(1″) is a linear, branched or cyclic C₁-C₈-alkyl group which may bearone or more identical or different fluorine, chlorine, OR² or NR² ₂substituents, a C₆-C₁₀-aryl group which may bear one or more identicalor different fluorine, chlorine, OR² or NR² ₂ substituents, aC₇-C₁₂-alkylaryl or arylalkyl group, where the alkyl part may bear oneor more identical or different fluorine, chlorine, OR² or NR² ₂substituents and the aryl part may bear fluorine, chlorine, OR² or NR² ₂substituents, a C₂-C₈-alkenyl group or C₂-C₈-alkynyl group which mayeach bear one or more identical or different fluorine, chlorine, OR² orNR² ₂ substituents, a C₈-C₁₂-arylalkenyl group which may bear one ormore identical or different fluorine, chlorine, OR² or NR² ₂substituents, a OR², SiR² ₃ or —OSiR² ₃ group, where R² are identical ordifferent and are each a C₁-C₄-alkyl or phenyl group, where the alkylgroup may bear one or more identical or different fluorine, chlorine,OR² or NR² ₂ substituents and the aryl group may bear fluorine,chlorine, OR² or NR² ₂ substituents, a C₂-C₁₆-heterocyclic group, wherepreferred heteroatoms are oxygen, nitrogen, sulfur and silicon, whichmay in turn bear C₁-C₁₀-radicals or heteroatoms as substituents, and

R^(3′) is an unsaturated C₂-C₂₀-group such as a C₆-C₁₄-aryl group whichmay bear fluorine, chlorine, OR², SR², NR² ₂, NH₂, NO₂, CN, COR² orCO₂R² substituents, a C₇-C₁₅-alkylaryl group or C₇-C₁₅-arylalkyl group,where the alkyl part may bear one or more identical or differentfluorine, OR², NR² ₂— or —OSiR² ₃ substituents and the aryl part maybear fluorine, chlorine, OR², SR², NR² ₂—, NH₂, NO₂, CN, COR² or CO₂R²substituents, a C₂-C₁₀-alkenyl group which may bear one or moreidentical or different fluorine, OR², CO₂R², COR², NR² ₂— or —OSiR² ₃substituents, a C₂-C₁₀-alkynyl group which may bear one or moreidentical or different fluorine, OR², NR² ₂— or —OSiR² ₃ substituents, aC₈-C₁₂-arylalkenyl group, a PR² ₂, B(OR²)₂ or SnR² ₃ group, where R² areidentical or different and are each a C₁-C₄-alkyl or C₆-aryl group,where the alkyl group may bear one or more identical or differentfluorine, chlorine, OR² or NR² ₂ substituents and the aryl group maybear fluorine, chlorine, OR² or NR² ₂ substituents, and, in addition,two radicals R² may be joined to one another to form a ring system, aC₁-C₁₄-heterocyclic group, where preferred heteroatoms are oxygen,nitrogen or sulfur which may in turn bear C₁-C₆-radicals or heteroatomsas substituents.

Very particular preference is given to indanones of the formula IV inwhich

R^(1″) is a linear, branched or cyclic C₁-C₈-alkyl group which may bearone or more identical or different fluorine, OR² or NR² ₂ substituents,a C₆-aryl group which may bear fluorine, OR² or NR² ₂ substituents, aC₇-C₁₀-alkylaryl or arylalkyl group, which may each bear fluorine,chlorine, OR² or NR² ₂ substituents, a C₂-C₈-alkenyl group, aC₂-C₈-alkynyl group which may bear fluorine, OR² or NR² ₂ substituents,a C₈-C₁₀-arylalkenyl group which may bear fluorine, OR² or NR² ₂substituents, an OR², SiR² ₃ or —OSiR² ₃ group, where R² are identicalor different and are each a C₁-C₄-alkyl or phenyl group which may bearfluorine, chlorine, OR^(2a) or NR^(2a) ₂ substituents, aC₂-C₉-heterocyclic group, where preferred heteroatoms are oxygen,nitrogen and sulfur, which may in turn bear C₁-C₆-hydrocarbon radicalsor heteroatoms as substituents, and

R^(3′) is an unsaturated C₂-C₁₄-group such as a C₆-C₁₄-aryl group whichmay bear fluorine, chlorine, R², OR^(2a) or NR^(2a) ₂ substituents, aC₇-C₁₀-alkylaryl group or C₇-C₁₀-arylalkyl group, where the alkyl partmay bear one or more identical or different fluorine, OR^(2a), NR^(2a) ₂or —OSiR^(2a) ₃ substituents and the aryl part may bear one or moreidentical or different fluorine, chlorine, OR^(2a) or NR^(2a) ₂substituents, a C₂-C₈-alkenyl group which may bear one or more identicalor different fluorine, OR^(2a), CO₂R^(2a) or NR^(2a) ₂ substituents, aC₂-C₈-alkynyl group which may bear one or more identical or differentfluorine, OR^(2a) or NR^(2a) ₂ substituents, a C₈-C₁₂-arylalkenyl group,a PR^(2a) ₂, B(OR^(2a))₂ or SnR^(2a) ₃ group, where R^(2a) are identicalor different and are each a linear or branched C₁-C₄-alkyl group whichmay bear one or more fluorine substituents or a phenyl group which maybear one or more identical or different fluorine or OR^(2a)substituents, and, in addition, two radicals R^(2a) may be joined to oneanother to form a ring system, a C₁-C₁₄-heterocyclic group, wherepreferred heteroatoms are oxygen, nitrogen or sulfur, which may in turnbear C₁-C₄-radicals or heteroatoms as substituents,

and Y¹⁰, Y¹¹ and Y¹² are each a hydrogen atom.

Illustrative examples of indanones of the formula IV, which do not,however, restrict the scope of the invention, are:

2-methyl-7-phenyl-1-indanone

2-methyl-7-(1-naphthyl)-1-indanone

2-methyl-7-(2-naphthyl)-1-indanone

2-methyl-7-(2-methyl-1-naphthyl)-1-indanone

2-methyl-7-(4-methyl-1-naphthyl)-1-indanone

2-methyl-7-(4-methoxy-1-naphthyl)-1-indanone

2-methyl-7-(6-methoxy-2-naphthyl)-1-indanone

2-methyl-7-(4-methylphenyl)-1-indanone

2-methyl-7-(3-methylphenyl)-1-indanone

2-methyl-7-(2-methylphenyl)-1-indanone

2-methyl-7-(3,5-dimethylphenyl)-1-indanone

2-methyl-7-(2,3-dimethylphenyl)-1-indanone

2-methyl-7-(2,4-dimethylphenyl)-1-indanone

2-methyl-7-(2,5-dimethylphenyl)-1-indanone

2-methyl-7-(3-butylphenyl)-1-indanone

2-methyl-7-(4-tert-butylphenyl)-1-indanone

2-methyl-7-mesityl-1-indanone

2-methyl-7-(4-biphenyl)-1-indanone

2-methyl-7-(3-biphenyl)-1-indanone

2-methyl-7-(2-biphenyl)-1-indanone

2-methyl-7-(3,5-diphenylphenyl)-1-indanone

2-methyl-7-(4-styryl)-1-indanone

2-methyl-7-(3-styryl)-1-indanone

2-methyl-7-(2-styryl)-1-indanone

2-methyl-7-(9-anthracenyl)-1-indanone

2-methyl-7-(9-phenanthrenyl)-1-indanone

2-methyl-7-(2-hydroxyphenyl)-1-indanone

2-methyl-7-(4-hydroxyphenyl)-1-indanone

2-methyl-7-(3-hydroxyphenyl)-1-indanone

2-methyl-7-(2,4-dihydroxyphenyl)-1-indanone

2-methyl-7-(3,5-dihydroxyphenyl)-1-indanone

2-methyl-7-(4-methoxyphenyl)-1-indanone

2-methyl-7-(3-methoxyphenyl)-1-indanone

2-methyl-7-(2-methoxyphenyl)-1-indanone

2-methyl-7-(2,4-dimethoxyphenyl)-1-indanone

2-methyl-7-(3,5-dimethoxyphenyl)-1-indanone

2-methyl-7-(3,4,5-trimethoxyphenyl)-1-indanone

2-methyl-7-(4-phenoxyphenyl)-1-indanone

2-methyl-7-(3,4-methylenedioxy)phenyl)-1-indanone

2-methyl-7-(4-thioanisyl)-1-indanone

2-methyl-7-(3-thioanisyl)-1-indanone

2-methyl-7-(4-nitrophenyl)-1-indanone

2-methyl-7-(3-nitrophenyl)-1-indanone

2-methyl-7-(2-nitrophenyl)-1-indanone

2-methyl-7-(4-methyl-3-nitrophenyl)-1-indanone

2-methyl-7-(4-methoxycarbonylphenyl)-1-indanone

2-methyl-7-(3-methoxycarbonylphenyl)-1-indanone

2-methyl-7-(2-methoxycarbonylphenyl)-1-indanone

2-methyl-7-(4-carboxylphenyl)-1-indanone

2-methyl-7-(2-carboxylphenyl)-1-indanone

2-methyl-7-(4-formylphenyl)-1-indanone

2-methyl-7-(4-acetylphenyl)-1-indanone

2-methyl-7-(4-pivaloylphenyl)-1-indanone

2-methyl-7-(4-aminophenyl)-1-indanone

2-methyl-7-(3-aminophenyl)-1-indanone

2-methyl-7-(2-aminophenyl)-1-indanone

2-methyl-7-(4-dimethylaminophenyl)-1-indanone

2-methyl-7-(3-dimethylaminophenyl)-1-indanone

2-methyl-7-(4-(1-pyrrolidino)phenyl)-1-indanone

2-methyl-7-(4-hydrazinophenyl)-1-indanone

2-methyl-7-(4-cyanophenyl)-1-indanone

2-methyl-7-(3-cyanophenyl)-1-indanone

2-methyl-7-(2-cyanophenyl)-1-indanone

2-methyl-7-(4-trifluoromethoxyphenyl)-1-indanone

2-methyl-7-(4-fluorophenyl)-1-indanone

2-methyl-7-(4-bromophenyl)-1-indanone

2-methyl-7-(2,4-difluorophenyl)-1-indanone

2-methyl-7-(4-chlorophenyl)-1-indanone

2-methyl-7-(3,5-dichlorophenyl)-1-indanone

2-methyl-7-(4-trifluoromethylphenyl)-1-indanone

2-methyl-7-(3-trifluoromethylphenyl)-1-indanone

2-methyl-7-(3,5-bis(trifluoromethyl)phenyl)-1-indanone

2-methyl-7-(2,4-bis(trifluoromethyl)phenyl)-1-indanone

2-methyl-7-(2-furyl)-1-indanone

2-methyl-7-(3-furyl)-1-indanone

2-methyl-7-(5-methyl-2-furyl)-1-indanone

2-methyl-7-(benzofuryl)-1-indanone

2-methyl-7-(2-thiophenyl)-1-indanone

2-methyl-7-(5-methyl-2-thiophenyl)-1-indanone

2-methyl-7-(3-thiophenyl)-1-indanone

2-methyl-7-(5-isobutyl-2-thiophenyl)-1-indanone

2-methyl-7-(benzothiophenyl)-1-indanone

2-methyl-7-(N-methyl-2-pyrrolyl)-1-indanone

2-methyl-7-(N-methyl-3-pyrrolyl)-1-indanone

2-methyl-7-(2-pyridyl)-1-indanone

2-methyl-7-(3-pyridyl)-1-indanone

2-methyl-7-(4-pyridyl)-1-indanone

2-methyl-7-(2-pyrimidyl)-1-indanone

2-methyl-7-(2-quinolyl)-1-indanone

2-methyl-7-(3-quinolyl)-1-indanone

2-methyl-7-(4-isoquinolyl)-1-indanone

2-methyl-7-(2-thiazolyl)-1-indanone

2-methyl-7-(2-benzothiazolyl)-1-indanone

2-methyl-7-(2-N-methylimidazolyl)-1-indanone

2-methyl-7-(2-N-methylbenzoimidazolyl)-1-indanone

2-methyl-7-(2-oxazolyl)-1-indanone

2-methyl-7-(N-methyltriazolyl)-1-indanone

2-methyl-7-benzyl-1-indanone

2-methyl-7-(hex-1-en-6-yl)-1-indanone

2-methyl-7-(hex-1-en-1-yl)-1-indanone

2-methyl-7-vinyl-1-indanone

2-methyl-7-(2-trimethylsilylethen-1-yl)-1-indanone

2-methyl-7-(2-phenylethyn-1-yl)-1-indanone

2-methyl-7-(2-tert-butylethyn-1-yl)-1-indanone

2-methyl-7-allyl-1-indanone

2-methyl-7-(2-trimethylsilylethyn-1-yl)-1-indanone

2-methyl-7-(2-phenylethen-1-yl)-1-indanone

2-methyl-7-trimethylstannyl-1-indanone

2-methyl-7-tributylstannyl-1-indanone

2-methyl-7-triphenylstannyl-1-indanone

2-methyl-7-(boronic acid pinacol ester)-1-indanone

2-methyl-7-(boronic acid trimethylene glycol ester)-1-indanone

2-methyl-7-(B-catecholborane)-1-indanone

2-methyl-7-diphenylphosphino-1-indanone

2-methyl-7-dibutylphosphino-1-indanone

2-methyl-7-(methoxyphenyl-methyl-phosphino)-1-indanone

2-ethyl-7-phenyl-1-indanone

2-ethyl-7-(4-tolyl)-1-indanone

2-ethyl-7-naphthyl-1-indanone

2-ethyl-7-(2-furyl)-1-indanone

2-isopropyl-7-(2-pyridyl)-1-indanone

2-isopropyl-7-phenyl-1-indanone

2-isopropyl-7-naphthyl-1-indanone

2-isobutyl-7-phenyl-1-indanone

2-isobutyl-7-naphthyl-1-indanone

2-cyclohexyl-7-phenyl-1-indanone

2-trifluoromethyl-7-phenyl-1-indanone

2-trifluoromethyl-7-(4-tolyl)-1-indanone

2-trifluoromethyl-7-naphthyl-1-indanone

2-trifluoromethyl-7-(4-methoxyphenyl)-1-indanone

2-trifluoromethyl-7-(3,5-bis(trifluoromethyl)phenyl)-1-indanone

2-methyl-4-methoxy-7-phenyl-1-indanone

2,6-dimethyl-7-phenyl-1-indanone

2,5-dimethyl-7-phenyl-1-indanone

2,5-dimethyl-7-p-tolyl-1-indanone

2,5-dimethyl-7-(2-thiophenyl)-1-indanone

2-methyl-5-phenyl-7-naphthyl-1-indanone

2-methyl-5,7-diphenyl-1-indanone

2-methyl-7-(4-fluorophenyl)-1-indanone

2-methyl-5-diphenylphosphino-7-(4-nitrophenyl)-1-indanone

2-methyl-5-chloro-7-phenyl-1-indanone

2,6-dimethyl-7-(4-methoxyphenyl)-1-indanone

2-ethyl-5-vinyl-7-(2-furyl)-1-indanone

2-isopropyl-5-trifluoromethyl-7-phenyl-1-indanone

2-cyclohexyl-5-methyl-7-(2-pyridyl)-1-indanone

2-trifluoromethyl-7-naphthyl-1-indanone

2-trimethylsilyl-5-isopropyl-7-(boronic acid pinacol ester)-1-indanone

2-dimethylamino-6-cyclohexyl-7-trimethylstannyl-1-indanone

2-ethyl-7-(9-phenanthrenyl)-1-indanone

2-ethyl-7-(2-pyridyl)-1-indanone

2-butyl-7-phenyl-1-indanone

2-butyl-7-(4-tolyl)-1-indanone

2-butyl-7-naphthyl-1-indanone

2-butyl-7-(2-furyl)-1-indanone

2-butyl-7-(p-phenanthrenyl)-1-indanone

2-butyl-7-(2-pyridyl)-1-indanone

2-ethyl-7-(4-tert-butylphenyl)-1-indanone

2-n-propyl-7-phenyl-1-indanone

2-n-propyl-7-naphthyl-1-indanone

2-n-propyl-7-(4-tert-butylphenyl)-1-indanone

2-n-propyl-7-(4-methylphenyl)-1-indanone

2-n-butyl-7-phenyl-1-indanone

2-n-butyl-7-naphthyl-1-indanone

2-n-butyl-7-(4-tert-butylphenyl)-1-indanone

2-n-butyl-7-(4-methylphenyl)-1-indanone

Both indanones of the formulae I and Ia and also indanones of theformulae II and IIa are suitable, inter alia, as intermediates in thepreparation of metallocenes and active compounds in the fields ofpharmacy and crop protection.

The indanones of the formulae II and IIa can easily be converted intothe indenes of the formulae V and Va by literature methods (eg.: R. C.Larock, Comprehensive Organic Transformations, VCH, 1989, EP 0 629 632A2).

In the formulae II, IIa, V and Va, the radicals R¹, R³, Y⁴, Y⁵ and Y⁶are as defined above for formulae II and IIa.

Metallocenes can be prepared from the indenes of the formulae V and Vaby literature methods (eg. EP 576 970, EP 629 632). Preference is givento unbridged or bridged metallocenes of the formula (VI)

where R¹, R³, Y⁴, Y⁵ and Y⁶ are as defined above for formula II,

M is a transition element of group 4, 5 or 6 of the Periodic Table ofthe Elements, eg. titanium, zirconium, hafnium, vanadium, niobium,tantalum, chromium, molybdenum, tungsten, preferably titanium,zirconium, hafnium, particularly preferably zirconium,

R⁹ and R¹⁰ are identical or different and are each a hydrogen atom,hydroxy or a halogen atom or a C₁-C₄₀-group such as C₁-C₁₀-alkyl,C₁-C₁₀-alkoxy, C₆-C₁₀-aryl, C₆-C₁₀-aryloxy, C₂-C₁₀-alkenyl,C₇-C₄₀-arylalkyl, C₇-C₄₀-alkylaryl, C₈-C₄₀-arylalkenyl, preferablyhydrogen, C₁-C₃-alkyl, in particular methyl, C₁-C₃-alkoxy, C₆-aryl,C₆-aryloxy, C₂-C₁₀-alkenyl, C₇-C₁₀-arylalkyl, C₇-C₁₀-alkylaryl,C₈-C₁₀-arylalkenyl or a halogen atom, in particular chlorine,

x is zero or 1,

R¹¹ is a bridge such as

where M² is carbon, silicon, germanium or tin, preferably silicon orcarbon, in particular silicon,

p is 1, 2 or 3, preferably 1 or 2, in particular 1,

R¹² and R¹³ are identical or different and are each a hydrogen atom, ahalogen atom or a C₁-C₂₀-group such as C₁-C₂₀-alkyl, C₆-C₁₄-aryl,C₁-C₁₀-alkoxy, C₂-C₁₀-alkenyl, C₇-C₂₀-arylalkyl, C₇-C₂₀-alkylaryl,C₆-C₁₀-aryloxy, C₁-C₁₀-fluoroalkyl, C₆-C₁₀-haloaryl or C₂-C₁₀-alkynyl or

R¹² and R¹³ together with the atom connecting them form a ring;preferably, R¹² and R¹³ are hydrogen, C₁-C₆-alkyl, C₆-C₁₀-aryl,C₁-C₆-alkoxy, C₂-C₄-alkenyl, C₇-C₁₀-arylalkyl, C₇-C₁₀-alkylaryl,particularly preferably C₁-C₆-alkyl or C₆-C₁₀-aryl, or R¹² and R¹³together with the atom connecting them form a ring.

R³ are identical or different, preferably identical, and are preferablyeach a C₆-C₄₀-aryl group which may contain heteroatoms. Preference isgiven to C₆-C₄₀-aryl groups which may be halogenated, in particularfluorinated, or may bear halogenated, in particular fluorinated,C₁-C₂₀-hydrocarbon radicals. R³ are particularly preferably each aphenyl, naphthyl, phenanthryl or anthracenyl group which is fluorinatedand/or bears fluorinated, in particular perfluorinated,C₁-C₁₀-hydrocarbon radicals such as CF₃ or C₂F₅.

Particularly suitable metallocenes of the formula VI comprise thefollowing molecular fragments:

-   MR⁹R¹⁰: ZrCL₂, Zr(CH₃)₂, HfCl₂, Hf(CH₃)₂-   R¹: linear C₁-C₁₀-alkyl-   Y⁴, Y², Y⁶: hydrogen-   R³: 4-(C₄-C₈-alkyl)phenyl, where the 4-(C₄-C₈-alkyl) group is    preferably a branched C₄-C₈-alkyl group, in particular a tert-butyl    group,-   R¹¹: dimethylsilyl, diphenylsilyl, methylphenylsilyl.

Further preferred metallocene components of the metallocenes of theformula VI are combinations of the following molecular fragments:

-   MR⁹R¹⁰: ZrCl₂, Zr(CH₃)₂,-   R¹: C₁-C₄-alkyl such as methyl, ethyl, isopropyl, n-butyl,    sec-butyl,-   Y⁶: hydrogen-   Y⁴, Y⁵: hydrogen, C₁-C₄-alkyl, C₆-C₁₀-aryl,-   R³: 4-fluorophenyl, 3,5-difluorophenyl, pentafluorophenyl,    4-trifluoromethylphenyl, 3-trifluoromethylphenyl,    2-trifluoromethylphenyl, 3,5-ditrifluoromethylphenyl,    2,6-ditrifluoromethylphenyl, pentatrifluoromethylphenyl,    4-pentafluoroethylphenyl, 3-pentafluoroethylphenyl,    2-pentafluoroethylphenyl, 3,5-dipentafluoroethylphenyl,    2,6-dipentafluoroethylphenyl, mono-, di-, tri- and    tetrafluoronaphthyl, penta(pentafluoroethyl)phenyl,

R¹¹: dimethylsilanediyl, dimethylgermanediyl, CH₂—CH₂, CH(CH₃)—CH₂,CH(CH₃)—CH(CH₃), C(CH₃)₂—CH₂, C(CH₃)₂—C(CH₃)₂.

Radicals having the same designation on the two indenyl ligands can beidentical to or different from one another. Thus, the two indenylligands can be identical or can be different from one another (eg. whenone Y⁶=H, and the other Y⁶=CH₃ or when one Y⁶=CH₃ and the otherY⁶=C₂H₅).

Illustrative examples of metallocenes which can be prepared, which donot, however, restrict the scope of the invention, are:

dimethylsilanediylbis(2-methyl-4-(4-fluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(3,5-difluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(2,6-difluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(pentafluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(4-trifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(3,5-ditrifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(2,6-ditrifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(pentatrifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(4-pentafluoroethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(3,5-dipentafluoroethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(2,6-dipentafluoroethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(penta(pentafluoroethyl)phenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(3,5-difluorophenyl)-6-phenylindenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(3,5-difluoromethylphenyl)-6-phenylindenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(4-pentafluoroethylphenyl)-6-phenylindenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(3,5-dipentafluoroethylphenyl)-6-phenylindenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(pentafluorophenyl)-6-phenylindenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(3,5-ditrifluoromethylphenyl)-6-methylindenyl)ZrCl₂

dimethylsilanediylbis(2-methyl-4-(3,5-ditrifluoromethylphenyl)-6-isopropylindenyl)ZrCl₂

dimethylsilanediylbis[1-(2-n-propyl-4-(4-tert-butylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-n-butyl-4-(4-tert-butylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-n-pentyl-4-(4-tert-butylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis(2-n-butyl-4-(3,5-difluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-n-butyl-4-(4-trifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-n-butyl-4-(3,5-ditrifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-n-butyl-4-(4-pentafluoroethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-n-butyl-4-(3,5-dipentafluoroethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-n-butyl-4-(pentafluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-n-butyl-4-(3,5-difluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-n-butyl-4-(pentafluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-sec-butyl-4-(3,5-difluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-sec-butyl-4-(4-trifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-sec-butyl-4-(3,5-ditrifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-sec-butyl-4-(4-pentafluoroethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-sec-butyl-4-(3,5-dipentafluoroethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-sec-butyl-4-(pentafluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-sec-butyl-4-(3,5-difluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-sec-butyl-4-(pentafluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-isobutyl-4-(3,5-difluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-isobutyl-4-(4-trifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-isobutyl-4-(3,5-ditrifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-isobutyl-4-(4-pentafluoroethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-isobutyl-4-(3,5-dipentafluoroethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-isobutyl-4-(pentafluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-ethyl-4-(3,5-difluorophenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-ethyl-4-(4-trifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-ethyl-4-(3,5-ditrifluoromethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-ethyl-4-(4-pentafluoroethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-ethyl-4-(3,5-dipentafluoroethylphenyl)indenyl)ZrCl₂

dimethylsilanediylbis(2-ethyl-4-(pentafluorophenyl)indenyl)ZrCl₂

1,2-ethanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride

1,2-ethanediylbis(2-ethyl-4-phenylindenyl)zirconium dichloride

1,2-ethanediylbis(2-isobutyl-4-phenylindenyl)zirconium dichloride

1,2-ethanediylbis(2-n-butyl-4-phenylindenyl)zirconium dichloride

1,2-ethanediylbis(2-sec-butyl-4-phenylindenyl)zirconium dichloride

1,2-ethanediylbis(2-methyl-4-(1-naphthyl)indenyl)zirconium dichloride

1,2-ethanediylbis(2-ethyl-4-(1-naphthyl)indenyl)zirconium dichloride

1,2-ethanediylbis(2-isobutyl-4-(1-naphthyl)indenyl)zirconium dichloride

1,2-ethanediylbis(2-n-butyl-4-(1-naphthyl)indenyl)zirconium dichloride

1,2-ethanediylbis(2-sec-butyl-4-(1-naphthyl)indenyl)zirconium dichloride

1,2-ethanediylbis(2-methyl-4-(2-naphthyl)indenyl)zirconium dichloride

1,2-ethanediylbis(2-ethyl-4-(2-naphthyl)indenyl)zirconium dichloride

1,2-ethanediylbis(2-isobutyl-4-(2-naphthyl)indenyl)zirconium dichloride

1,2-ethanediylbis(2-n-butyl-4-(2-naphthyl)indenyl)zirconium dichloride

1,2-ethanediylbis(2-sec-butyl-4-(2-naphthyl)indenyl)zirconium dichloride

1,2-ethanediylbis(2-methyl-4-phenanthrylindenyl)zirconium dichloride

1,2-ethanediylbis(2-ethyl-4-phenanthrylindenyl)zirconium dichloride

1,2-ethanediylbis(2-isobutyl-4-phenanthrylindenyl)zirconium dichloride

1,2-ethanediylbis(2-n-butyl-4-phenanthrylindenyl)zirconium dichloride

1,2-ethanediylbis(2-sec-butyl-4-phenanthrylindenyl)zirconium dichloride

1,2-ethanediylbis(2-methyl-4-(3,5-dimethylphenyl)indenyl)zirconiumdichloride

1,2-ethanediylbis(2-ethyl-4-(3,5-dimethylphenyl)indenyl)zirconiumdichloride

1,2-ethanediylbis(2-n-butyl-4-(3,5-dimethylphenyl)indenyl)zirconiumdichloride

1,2-ethanediylbis(2-sec-butyl-4-(3,5-dimethylphenyl)indenyl)zirconiumdichloride

1,2-ethanediylbis(2-methyl-4-(4-methylphenyl)indenyl)zirconiumdichloride

1,2-ethanediylbis(2-ethyl-4-(4-methylphenyl)indenyl)zirconium dichloride

1,2-ethanediylbis(2-isobutyl-4-(4-methylphenyl)indenyl)zirconiumdichloride

1,2-ethanediylbis(2-n-butyl-4-(4-methylphenyl)indenyl)zirconiumdichloride

1,2-ethanediylbis(2-sec-butyl-4-(4-methylphenyl)indenyl)zirconiumdichloride

1,2-ethanediylbis(2-methyl-4-anthracenylindenyl)zirconium dichloride

1,2-ethanediylbis(2-ethyl-4-anthracenylindenyl)zirconium dichloride

1,2-ethanediylbis(2-isobutyl-4-anthracenylindenyl)zirconium dichloride

1,2-ethanediylbis(2-n-butyl-4-anthracenylindenyl)zirconium dichloride

1,2-ethanediylbis(2-sec-butyl-4-anthracenylindenyl)zirconium dichloride

Also preferred are the corresponding dimethylzirconium compounds and thecorresponding compounds having a 1,2-(1-methylethanediyl),1,2-(1,1-dimethylethanediyl) or 1,2-(1,2-dimethylethanediyl) bridge.

dimethylsilanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-ethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-ethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-ethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-butylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-isopropylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-isopropylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-isopropylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-tert-butylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-tert-butylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-cyclohexylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-cyclohexylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-triisopropylsilylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-biphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-biphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-biphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-biphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-styryl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-styryl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-styryl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(9-anthracenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(9-phenanthrenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-methyl-1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-methyl-1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2,4-dimethylphenyl)indenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-methyl-4-(2,3-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3,5-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3,4-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2,6-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2,3,4-trimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3,4,5-trimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2,4,5-trimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2,3,4-trimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-mesitylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-methyl-4-(3,5-diphenylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3,5-diisopropylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2,4-dimethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3,5-dimethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3,4-dimethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3,4,5-trimethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2,4,6-trimethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-phenoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-isopropoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-fluorophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-fluorophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2,4-difluorophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3,5-difluorophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2,3,5,6-tetrafluoro-4-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-N,N-dimethylaminophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-N,N-dimethylaminophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-N,N-dimethylaminophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-(1-pyrrolidino)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-(1-piperidino)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2,4-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-trifluoromethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-methyl-4-trifluoromethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-pentafluoroethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-thioanisylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-thioanisylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-thioanisylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(4-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-pyrimidyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-furyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-furyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(5-methyl-2-furyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-benzofuryl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(5-methyl-2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(5-isobutyl-2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-benzothiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-thiazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-benzothiazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-oxazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(N-methyl-2-pyrrolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(N-methyl-3-pyrrolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-quinolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(3-quinolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(isoquinolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(N-methyltriazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(N-methyl-2-imidazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(N-methyl-2-benzoimidazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-butylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-methyl-4-cyclohexylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-isopropylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-benzylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-methyl-4-isobutylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(hex-1-en-6-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(hex-1-en-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-vinylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-phenylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-allylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-trimethylsilylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(2-phenylethen-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(diphenylphosphino)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(dibutylphosphino)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-(dimethylphosphino)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-phenylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-ethyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-ethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-ethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-ethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-butylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-isopropylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-isopropylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-isopropylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-tert-butylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-tert-butylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-cyclohexylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-cyclohexylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-triisopropylsilylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-biphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-biphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-biphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-biphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-styryl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-styryl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-styryl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(9-anthracenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(9-phenanthrenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-methyl-1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-methyl-1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2,4-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2,3-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3,5-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3,4-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2,6-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2,3,4-trimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3,4,5-trimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2,4,5-trimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2,3,4-trimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-mesitylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3,5-diphenylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3,5-diisopropylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2,4-dimethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3,5-dimethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3,4-dimethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3,4,5-trimethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2,4,6-trimethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-phenoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-n-propyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-n-propyl-4-naphthylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-n-propyl-4-(4-tert-butylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-n-propyl-4-p-tolylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-isopropoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-fluorophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-fluorophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2,4-difluorophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3,5-difluorophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2,3,5,6-tetrafluoro-4-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-N,N-dimethylaminophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-N,N-dimethylaminophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-N,N-dimethylaminophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-(1-pyrrolidino)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-(1-piperidino)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2,4-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-trifluoromethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-ethyl-4-trifluoromethoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-pentafluoroethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-thioanisylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-thioanisylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-thioanisylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(4-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-pyrimidyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-furyl)indenyl)]zirconiumdichloridedimethylsilanediylbis[1-(2-ethyl-4-(3-furyl)indenyl)]zirconiumdichloridedimethylsilanediylbis[1-(2-ethyl-4-(5-methyl-2-furyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-benzofuryl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(5-methyl-2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(5-isobutyl-2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-benzothiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-thiazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-benzothiazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-oxazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(N-methyl-2-pyrrolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(N-methyl-3-pyrrolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-quinolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(3-quinolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(isoquinolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(N-methyltriazole)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(N-methyl-2-imidazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(N-methyl-2-benzoimidazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-butylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-ethyl-4-cyclohexylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-isopropylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-benzylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-ethyl-4-isobutylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-ethyl-4-(hex-1-en-6-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(hex-1-en-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-vinylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-phenylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-allylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-trimethylsilylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(2-phenylethen-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(diphenylphosphino)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(dibutylphosphino)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4-(dimethylphosphino)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(3,5-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(4-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(2-furyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(2-oxazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-allylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-cyclohexylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,4-diisopropylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-isopropyl-4-butylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-benzylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(hex-1-en-6-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(hex-1-en-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-vinylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(2-phenylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(3,5-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(4-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(2-furyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(2-oxazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-allylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-isobutyl-4-cyclohexylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,4-diisobutylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-isobutyl-4-butylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-isobutyl-4-benzylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(hex-1-en-6-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(hex-1-en-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-vinylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(2-phenylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isobutyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(3,5-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(4-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-furyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-oxazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-allylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-cyclohexylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,4-bis(trifluoromethylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-butylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-benzylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(hex-1-en-6-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(hex-1-en-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-vinylindenyl)]-zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-phenylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trifluoromethyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,5-dimethyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,7-dimethyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,6-dimethyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,6-dimethyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,6-dimethyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,6-dimethyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,6-dimethyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,6-dimethyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,7-dimethyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,7-dimethyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,7-dimethyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-6-methoxy-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4,6-diphenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-4,6-diphenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-6-methyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-6-vinyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-6-benzyl-4-naphthylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-ethyl-5-methyl-4-(3,5-dimethylphenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-phenylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-phenyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(3,5-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(4-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(2-furyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(2-oxazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-allylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-phenyl-4-cyclohexylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,4-diphenylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-phenyl-4-butylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-phenyl-4-benzylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-phenyl-4-(hex-1-en-6-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(hex-1-en-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-vinylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-phenyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(2-phenylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-phenyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(3,5-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(4-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-furyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-oxazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-allylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-cyclohexylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,4-dicyclohexylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-butylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-benzylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(hex-1-en-6-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(hex-1-en-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-vinylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-phenylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-phenylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-butyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(3,5-dimethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(4-trifluoromethylphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(2-furyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(2-oxazolyl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-allylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-butyl-4-cyclohexylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,4-dibutylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-butyl-4-benzylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-butyl-4-(hex-1-en-6-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(hex-1-en-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-vinylindenyl)]zirconium dichloride

dimethylsilanediylbis[1-(2-butyl-4-(2-trimethylsilylethen-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(2-phenylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-butyl-4-(2-tert-butylethyn-1-yl)indenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium

dimethylsilanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium diethoxide

dimethylsilanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium diphenoxide

dimethylsilanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]dimethylzirconium

dimethylsilanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]dibenzylzirconium

dimethylsilanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconiumbis(dimethylamide)

dimethylsilanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconiumbis(diethylamide)

dimethylsilanediylbis[1-(2-methyl-4-(pyridyl)indenyl)]dimethylzirconium

dimethylsilanediylbis[1-(2-methyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]dimethylzirconium

dimethylsilanediylbis [1-(2-methyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconium dimethoxide

dimethylsilanediylbis[1-(2-ethyl-4-(3,5-dimethylphenyl)indenyl)]dimethylzirconium

dimethylsilanediylbis[1-(2-dimethylamino-4-phenylindenyl)]dimethylzirconium

dimethylsilanediylbis[1-(2-N-piperino-4-naphthylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-trimethylsilyl-4-cyclohexylindenyl)]dimethylzirconium

dimethylsilanediylbis[1-(2-trimethylsilyloxy-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,6-dimethyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-methyl-4,6-diphenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,5-dimethyl-4-naphthylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-cyclohexyl-6-methyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2,5,6-trimethyl-4-phenylindenyl)]zirconiumdichloride

dimethylsilanediylbis[1-(2-isopropyl-5,6-difluoro-4-phenylindenyl)]zirconiumdichloride

1,2-ethanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride

1,2-ethanediylbis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium

1,2-ethanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

1,2-ethanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

1,2-ethanediylbis[1-(2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

1,2-ethanediylbis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconium dichloride

1,2-ethanediylbis[1-(2-methyl-4-(2-furyl)indenyl)]zirconium dichloride

1,2-ethanediylbis[1-(2-methyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

1,2-ethanediylbis[1-(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

1,2-ethanediylbis[1-(2-methyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

1,2-ethanediylbis[1-(2-isobutyl-4-phenylindenyl)]zirconium dichloride

1,2-ethanediylbis[1-(2-methyl-4-(3-dimethylaminophenyl)indenyl)]zirconiumdichloride

1,2-butanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride

1,2-butanediylbis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium

1,2-butanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

1,2-butanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

1,2-butanediylbis[1-(2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

1,2-butanediylbis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconium dichloride

1,2-butanediylbis[1-(2-methyl-4-(2-furyl)indenyl)]zirconium dichloride

1,2-butanediylbis[1-(2-phenyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

1,2-butanediylbis[1-(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

1,2-butanediylbis[1-(2,5-dimethyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

1,2-butanediylbis[1-(2-isobutyl-4-phenylindenyl)]zirconium dichloride

1,2-butanediylbis[1-(2-methyl-4-(3-dimethylaminophenyl)indenyl)]zirconiumdichloride

bis[2-methyl-4-phenylindenyl]zirconium dichloride

bis[2-methyl-4-phenylindenyl]dimethylzirconium

bis[2-methyl-4-(1-naphthyl)indenyl]zirconium dichloride

bis[2-methyl-4-(2-naphthyl)indenyl]zirconium dichloride

bis[2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl]zirconiumdichloride

bis[2-butyl-4-(2-pyridyl)indenyl]zirconium dichloride

bis[2-methyl-4-(2-furyl)indenyl]zirconium dichloride

bis[2-methyl-4-(2-thiophenyl)indenyl]zirconium dichloride

bis[2-isopropyl-4-(4-methoxyphenyl)indenyl]zirconium dichloride

bis[2-methyl-4-(4-methylphenyl)indenyl]zirconium dichloride

bis[2-isobutyl-4-phenylindenyl]zirconium dichloride

bis[2-methyl-4-(3-dimethylaminophenyl)indenyl]zirconium dichloride

bis[2-methyl-4-(3,5-dimethylphenyl)indenyl]zirconium dichloride

bis[2-N-piperidino-4-(3,5-dimethylphenyl)indenyl]zirconium dichloride

[2-butyl-4-(2-pyridyl)indenyl]cyclopentadienylzirconium dichloride

[2-ethyl-4-(3,5-bis(trifluoromethyl)phenylindenyl]-[1-methylboratabenzene]zirconiumdichloride

[2-methyl-4-(3,5-dimethylphenyl)indenyl]fluorenylzirconium dichloride

[2-isobutyl-4-(4-methoxyphenyl)indenyl]-[2-methylindenyl]zirconiumdichloride

[2-cyclohexyl-4-(3-fluorophenylindenyl]trimethylcyclopentadienylzirconiumdichloride

[2-phenyl-4-(3-dimethylaminophenylindenyl]-[tert-butylmethylcyclopentadienyl]zirconiumdichloride

methylphenylsilanediylbis[1-(2-methyl-4-phenylindenyl)]zirconiumdichloride

methylphenylsilanediylbis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium

methylphenylsilanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

methylphenylsilanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

methylphenylsilanediylbis[1-(2-ethyl-4-(3,5-trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

methylphenylsilanediylbis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

methylphenylsilanediylbis[1-(2-methyl-4-(2-furyl)indenyl)]zirconiumdichloride

methylphenylsilanediylbis[1-(2-methyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

methylphenylsilanediylbis[1-(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

methylphenylsilanediylbis[1-(2-methyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

methylphenylsilanediylbis[1-(2-isobutyl-4-phenylindenyl)]zirconiumdichloride

methylphenylsilanediylbis[1-(2-methyl-4-(3-dimethylaminophenyl)indenyl)]zirconiumdichloride

isopropylidenebis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride

isopropylidenebis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium

isopropylidenebis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

isopropylidenebis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

isopropylidenebis[1-(2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

isopropylidenebis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconium dichloride

isopropylidenebis[1-(2-methyl-4-(2-furyl)indenyl)]zirconium dichloride

isopropylidenebis[1-(2-methyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

isopropylidenebis[1-(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

isopropylidenebis[1-(2-methyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

isopropylidenebis[1-(2-isobutyl-4-phenylindenyl)]zirconium dichloride

isopropylidenebis[1-(2-methyl-4-(3-dimethylaminophenyl)indenyl)]zirconiumdichloride

dimethylsilanediyl[1-(2-methyl-4-phenylindenyl)]cyclopentadienylzirconiumdichloride

dimethylsilanediyl[1-(2-methyl-4-phenylindenyl)]-[(1-(2-methylindenyl)]zirconiumdichloride

dimethylsilanediyl[1-(2-methyl-4-phenylindenyl)]trimethylcyclopentadienylzirconiumdichloride

dimethylsilanediyl[1-(2-methyl-4-phenylindenyl)]-[tert-butyl-methylcyclopentadienyl]zirconiumdichloride

dimethylsilanediyl[1-(2-methyl-4-phenylindenyl)]fluorenylzirconiumdichloride

dimethylsilanediyl[1-(2-ethyl-4-naphthylindenyl)]tetramethylcyclopentadienylzirconiumdichloride

dimethylsilanediyl[1-(2-methyl-4-(3,5-bistrifluoromethyl)indenyl)]cyclopentadienylzirconiumdichloride

dimethylsilanediyl[1-(2-methyl-4-(2-pyridyl)indenyl)]tetramethylcyclopentadienylzirconiumdichloride

dimethylsilanediyl[1-(2-methyl-4-(2,4-dimethoxyphenyl)indenyl)]-[1-methylboratabenzene]zirconiumdichloride

dimethylgermanediylbis[1-(2-methyl-4-phenylindenyl)]zirconium dichloride

dimethylgermanediylbis[1-(2-methyl-4-phenylindenyl)]dimethylzirconium

dimethylgermanediylbis[1-(2-methyl-4-(1-naphthyl)indenyl)]zirconiumdichloride

dimethylgermanediylbis[1-(2-methyl-4-(2-naphthyl)indenyl)]zirconiumdichloride

dimethylgermanediylbis[1-(2-ethyl-4-(3,5-bis(trifluoromethyl)phenyl)indenyl)]zirconiumdichloride

dimethylgermanediylbis[1-(2-butyl-4-(2-pyridyl)indenyl)]zirconiumdichloride

dimethylgermanediylbis[1-(2-methyl-4-(2-furyl)indenyl)]zirconiumdichloride

dimethylgermanediylbis[1-(2-methyl-4-(2-thiophenyl)indenyl)]zirconiumdichloride

dimethylgermanediylbis[1-(2-isopropyl-4-(4-methoxyphenyl)indenyl)]zirconiumdichloride

dimethylgermanediylbis[1-(2-methyl-4-(4-methylphenyl)indenyl)]zirconiumdichloride

dimethylgermanediylbis[1-(2-isobutyl-4-phenylindenyl)]zirconiumdichloride

dimethylgermanediylbis[1-(2-methyl-4-(3-dimethylaminophenyl)indenyl)]zirconiumdichloride

Further examples are the titanocenes and hafnocenes corresponding to thezirconocenes listed above.

The metallocenes which can be prepared from indanones via indenes arehighly active catalyst components for olefin polymerization. Dependingon the substitution pattern of the ligands, the metallocenes can beformed as a mixture of isomers. For the polymerization, the metallocenesare preferably used in isomerically pure form. The use of the racemateis sufficient in most cases.

However, it is also possible to use the pure enantiomer in the (+) or(−) form. An optically active polymer can be prepared using the pureenantiomers. However, the configurational isomers of the metallocenesshould be separated off, since the polymerization-active center (themetal atom) in these compounds usually produces a polymer havingdifferent properties. For certain applications, for example flexiblemoldings, this can be quite desirable.

The present invention therefore also provides a process for preparing apolyolefin by polymerization of at least one olefin in the presence of acatalyst comprising at least one cocatalyst and at least one stereorigidmetallocene compound of the formula I. For the purposes of the presentinvention, the term polymerization encompasses both homopolymerizationand copolymerization.

In the process of the present invention, preference is given topolymerizing one or more olefins of the formula R^(α)—CH═CH—R^(β), whereR^(α) and R^(β) are identical or different and are each a hydrogen atomor a hydrocarbon radical having from 1 to 20 carbon atoms, in particularfrom 1 to 10 carbon atoms, and R^(α) and R^(β) together with the atomsconnecting them may form one or more rings. Examples of such olefins are1-olefins having from 2 to 40 carbon atoms, preferably 2-10 carbonatoms, for example ethylene, propylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene or 1-octene, styrene, dienes such as 1,3-butadiene,isoprene, 1,4-hexadiene or cyclic olefins such as norbornene orethylidenenorbornene. In the process of the present invention,preference is given to homopolymerizing ethylene or propylene orcopolymerizing ethylene with one or more cyclic olefins such asnorbornene and/or one or more acyclic 1-olefins having from 3 to 20carbon atoms, eg. propylene, and/or one or more dienes having from 4 to20 carbon atoms, eg. 1,3-butadiene or 1,4-hexadiene. Examples of suchcopolymers are ethylene-norbornene copolymers, ethylene-propylenecopolymers and ethylene-propylene-1,4-hexadiene copolymers.

The polymerization is preferably carried out at from −60 to 250° C.,particularly preferably from 50 to 200° C. The pressure is preferablyfrom 0.5 to 2000 bar, particularly preferably from 5 to 64 bar.

The polymerization can be carried out in solution, in bulk, insuspension or in the gas phase, continuously or batchwise, in one ormore stages. Preferred embodiments are gas-phase and solutionpolymerization.

The catalyst used in the process of the present invention preferablycomprises one metallocene compound. It is also possible to use mixturesof two or more metallocene compounds, eg. for preparing polyolefinshaving a broad or multimodal molar mass distribution.

In principle, suitable cocatalysts for the process of the presentinvention are all compounds which, owing to their Lewis acidity, canconvert the neutral metallocene into a cation and stabilize the latter(“labile coordination”). Furthermore, the catalyst or the anion formedtherefrom should undergo no further reactions with the metallocenecation formed (EP 427 697). The cocatalyst used is preferably analuminum compound and/or a boron compound.

The boron compound preferably has the formula R^(a) _(x)NH_(4−x)BR^(b)₄, R^(a) _(x)PH_(4−x)BR^(b) ₄, R^(a) ₃CBR^(b) ₄ or BR^(b) ₃, where x isfrom 1 to 4, preferably 3, the radicals R^(a) are identical ordifferent, preferably identical, and are C₁-C₁₀-alkyl or C₈-C₁₈-aryl ortwo radicals R^(a) together with the atoms connecting them form a ring,and the radicals R^(b) are identical or different, preferably identical,and are C₆-C₁₈-aryl which may be substituted by alkyl, haloalkyl orfluorine. In particular, R^(a) is ethyl, propyl, butyl or phenyl andR^(b) is phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl,mesityl, xylyl or tolyl (EP 277 003, EP 277 004 and EP 426 638).

As cocatalyst, preference is given to using an aluminum compound such asaluminoxane and/or an aluminum alkyl.

The cocatalyst used is particularly preferably an aluminoxane, inparticular of the formula C for the linear type and/or the formula D forthe cyclic type,

where, in the formulae C and D, the radicals R^(c) are identical ordifferent and are each hydrogen or a C₁-C₂₀-hydrocarbon group such as aC₁-C₁₈-alkyl group, a C₆-C₁₈-aryl group or benzyl, and p is an integerfrom 2 to 50, preferably from 10 to 35.

Preferably, the radicals R^(c) are identical and are hydrogen, methyl,isobutyl, phenyl or benzyl, particularly preferably methyl.

If the radicals R^(c) are different, they are preferably methyl andhydrogen or alternatively methyl and isobutyl, with hydrogen or isobutylpreferably being present in a numerical proportion of from 0.01 to 40%(of the radicals R^(c)).

The methods of preparing the aluminoxanes are known. The precise spatialstructure of the aluminoxanes is not known (J. Am. Chem. Soc. (1993)115, 4971). For example, it is conceivable that chains and rings arejoined to form larger two-dimensional or three-dimensional structures.

Regardless of the method of preparation, all aluminoxane solutions havein common a variable content of unreacted aluminum starting compoundwhich is present in free form or as adduct.

It is possible to preactivate the metallocene compound with acocatalyst, in particular an aluminoxane, before use in thepolymerization reaction. This significantly increases the polymerizationactivity. The preactivation of the metallocene compound is preferablycarried out in solution. Here, the metallocene compound is preferablydissolved in a solution of the aluminoxane in an inert hydrocarbon.Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons.Preference is given to using toluene.

The concentration of the aluminoxane in the solution is in the rangefrom about 1% by weight to the saturation limit, preferably from 5 to30% by weight, in each case based on the total amount of solution. Themetallocene can be used in the same concentration but it is preferablyused in an amount of from 10⁻⁴ to 1 mol per mol of aluminoxane. Thepreactivation time is from 5 minutes to 60 hours, preferably from 5 to60 minutes. The preactivation is carried out at from −78 to 100° C.,preferably from 0 to 80° C.

The metallocene compound is preferably employed in a concentration,based on the transition metal, of from 10⁻³ to 10⁻⁸ mol, preferably from10⁻⁴ to 10⁻⁷ mol, of transition metal per dm³ of solvent or per dm³ ofreactor volume. The aluminoxane is preferably used in a concentration offrom 10⁻⁶ to 10⁻¹ mol, preferably from 10⁻⁵ to 10⁻² mol, per dm³ ofsolvent or per dm³ of reactor volume. The other cocatalysts mentionedare used in approximately equimolar amounts to the metallocene compound.However, higher concentrations are also possible in principle.

The aluminoxane can be prepared in various ways by known methods. One ofthe methods is, for example, reacting an aluminum-hydrocarbon compoundand/or a hydridoaluminum-hydrocarbon compound with water (gaseous,solid, liquid or bound—for example as water of crystallization) in aninert solvent (for example toluene). To prepare an aluminoxane havingdifferent radicals R^(c), for example, two different aluminum trialkylscorresponding to the desired composition are reacted with water.

To remove catalyst poisons present in the olefin, a purification stepusing an aluminum compound, preferably an aluminum alkyl such astrimethylaluminum or triethylaluminum, is advantageous. Thispurification can be carried out either in the polymerization systemitself or the olefin is brought into contact with the aluminum compoundand subsequently separated off again before addition to thepolymerization system.

As molar mass regulator and/or to increase the catalyst activity,hydrogen can be added in the process of the present invention. Thismakes it possible to obtain low molecular weight polyolefins such aswaxes.

In the process of the present invention, the metallocene compound ispreferably reacted with the cocatalyst outside the polymerizationreactor in a separate step using a suitable solvent. In this step, thecatalyst can be applied to a support.

In the process of the present invention, a prepolymerization can becarried out by means of the metallocene compound. The prepolymerizationis preferably carried out using the (or one of the) olefin(s) used inthe polymerization.

The catalyst used in the process of the present invention can besupported. The application to a support enables, for example, theparticle morphology of the polyolefin prepared to be controlled. Here,the metallocene compound can be reacted first with the support andsubsequently with the cocatalyst. The cocatalyst can also be supportedfirst and subsequently reacted with the metallocene compound. It is alsopossible to apply the reaction product of metallocene compound andcocatalyst to a support. Suitable support materials are, for example,silica gels, aluminum oxides, solid aluminoxane or other inorganicsupport materials such as magnesium chloride. Another suitable supportmaterial is a polyolefin powder in finely divided form. The supportedcocatalyst can be prepared, for example, as described in EP 567 952.

Preferably, the cocatalyst, eg. aluminoxane, is applied to a supportsuch as silica gels, aluminum oxides, solid aluminoxane, other inorganicsupport materials or else a polyolefin powder in finely divided form andthen reacted with the metallocene.

As inorganic supports, it is possible to use oxides which have beenproduced flame-pyrolytically by combustion of element halides in ahydrogen/oxygen flame or can be prepared as silica gels havingparticular particle size distributions and particle shapes.

The preparation of the supported cocatalyst can be carried out, forexample, as described in EP 578 838 in the following manner in astainless steel reactor having an explosion-proof design with a pumpedcirculation system and a pressure rating of 60 bar, with inert gassupply, temperature control by means of jacket cooling and a secondcooling circuit via a heat exchanger on the pumped circulation system.The pumped circulation system draws in the reactor contents via aconnection in the bottom of the reactor by means of a pump and pushes itinto a mixer and through a riser line via a heat exchanger back into thereactor. The mixer is configured such that in the inlet there is locateda constricted tube cross section where the flow velocity is increasedand into the turbulence zone of which there is introduced, axially andopposite to the flow direction, a thin feed line through which, pulsed,a defined amount of water under bar of argon can be fed in. The reactionis monitored by means of a sampler on the pumped circulation system.

However, other reactors are also suitable in principle.

The above-described reactor having a volume of 16 dm³ is charged with 5dm³ of decane under inert conditions. 0.5 dm³ (=5.2 mol) oftrimethylaluminum are added at 25° C. 250 g of silica gel SD 3216-30(Grace AG), which have been dried beforehand at 120° C. in anargon-fluidized bed, are then introduced into the reactor through asolids funnel and are homogeneously distributed by means of the stirrerand the pumped circulation system. A total amount of 76.5 g of water isadded to the reactor in portions of 0.1 cm³ every 15 seconds over aperiod of 3.25 hours. The pressure, caused by the argon and the gasesevolved, is kept constant at 10 bar by means of a pressure regulationvalve. After all the water has been introduced, the pumped circulationsystem is switched off and stirring is continued for another 5 hours at25° C.

The supported cocatalyst prepared in this way is used as a 10% strengthsuspension in n-decane. The aluminum content is 1.06 mmol of Al per cm³of suspension. The isolated solid contains 31% by weight of aluminum andthe suspension medium contains 0.1% by weight of aluminum.

Further possible ways of preparing a supported cocatalyst are describedin EP 578 838.

The metallocene of the present invention is then applied to thesupported cocatalyst by stirring the dissolved metallocene with thesupported cocatalyst. The solvent is removed and replaced by ahydrocarbon in which both cocatalyst and the metallocene are insoluble.

The reaction to form the supported catalyst system is carried out atfrom −20 to +120° C., preferably from 0 to 100° C., particularlypreferably from 15 to 40° C. The metallocene is reacted with thesupported cocatalyst by combining the cocatalyst as a suspension havinga concentration of from 1 to 40% by weight, preferably from 5 to 20% byweight, in an aliphatic, inert suspension medium such as n-decane,hexane, heptane or diesel oil with a solution of the metallocene in aninert solvent such as toluene, hexane, heptane or dichloromethane orwith the finely milled solid metallocene. Conversely, a solution of themetallocene can also be reacted with the solid cocatalyst.

The reaction is carried out by intensive mixing, for example bystirring, at a molar Al/M¹ ratio of from 100/1 to 10,000/1, preferablyfrom 100/1 to 3000/1, and a reaction time of from 5 to 120 minutes,preferably from 10 to 60 minutes, particularly preferably from 10 to 30minutes, under inert conditions. During the reaction time for preparingthe supported catalyst system, particularly when using the metallocenesof the present invention having absorption maxima in the visible region,changes occur in the color of the reaction mixture and these enable theprogress of the reaction to be followed.

After the reaction time has expired, the supernatant solution isseparated off, for example by filtration or decantation. The remainingsolid is washed from 1 to 5 times with an inert suspension medium suchas toluene, n-decane, hexane, diesel oil or dichloromethane to removesoluble constituents in the catalyst formed, in particular to removeunreacted and therefore soluble metallocene.

The supported catalyst system prepared in this way can be resuspended asvacuum-dried powder or while still moist with solvent and metered intothe polymerization system as a suspension in one of the abovementionedinert suspension media.

If the polymerization is carried out as a suspension or solutionpolymerization, an inert solvent customary for the Ziegler low-pressureprocess is used. For example, the polymerization is carried out in analiphatic or cycloaliphatic hydrocarbon, for example propane, butane,hexane, heptane, isooctane, cyclohexane or methylcyclohexane. It is alsopossible to use a petroleum or hydrogenated diesel oil fraction. Toluenecan also be used. Preference is given to carrying out the polymerizationin the liquid monomer.

Before addition of the catalyst, in particular the supported catalystsystem (comprising the metallocene of the present invention and asupported cocatalyst), it is possible to introduce, in addition, anotheraluminum alkyl compound such as trimethylaluminum, triethylaluminum,triisobutylaluminum, trioctylaluminum or isoprenylaluminum into thereactor to make the polymerization system inert (for example to removecatalyst poisons present in the olefin). This is added to thepolymerization system in a concentration of from 100 to 0.01 mmol of Alper kg of reactor contents. Preference is given to triisobutylaluminumand triethylaluminum in a concentration of from 10 to 0.1 mmol of Al perkg of reactor contents. This makes it possible to select a small molarAl/M¹ ratio in the synthesis of a supported catalyst system. If inertsolvents are used, the monomers are metered in in gaseous or liquidform.

The following abbreviations are used in the present application:

acac acetylacetonate 9-BBN 9-borabicyclo[3.3.1]nonane Bn benzyl Bu butyli-Bu isobutyl ^(t)Bu tertiary butyl COD 1,5-cyclooctadiene dbadibenzylideneacetone DBU 1,8-diazabicyclo[5.4.0]undec-7-ene diglymediethylene glycol dimethyl ether DME 1,2-dimethoxyethane DMFdimethylformamide dppe 1,2-bis(diphenylphosphino)ethane dppf1,1'-bis(diphenylphosphino)ferrocene dppp1,3-bis(diphenylphosphino)propane Et ethyl HMPA hexamethylphosphoramideMe methyl MTBE methyl tert-butyl ether NMP N-methyl-2-pyrrolidinonenonaflate nonafluorobutylsulfonate OAc acetate Ph phenyl PTE PeriodicTable of the Elements Tf trifluoromethanesulfonate THF tetrahydrofuranTMSCl trimethylsilyl chloride triflate trifluoromethanesulfonatetriglyme triethylene glycol dimethyl ether

EXAMPLES

The invention is illustrated by the following examples which do notrestrict the scope of the invention.

1. 7-Chloro-2-methyl-1-indanone (1)

50 g (0.3 mol) of 2-chloropropiophenone (B. L. Jenson et al.,Tetrahedron, 1978, 1627) together with 24.55 ml (0.33) of 37% strengthformaldehyde solution were placed in the reaction vessel. A solution of12 g of sodium hydroxide in 600 ml of water was added thereto. Themixture was stirred for 2.5 hours at 40° C. The phases were separated,the aqueous phase was extracted 3 times with 50 ml each time ofmethylene chloride, the combined organic phases were washed with 100 mlof 1N HCl solution and dried over magnesium sulfate. The methylenechloride solution was added while stirring to 400 g of hot (65° C.)concentrated sulfuric acid over a period of 2.25 hours. The methylenechloride distilled off during this procedure. After the addition wascomplete, stirring was continued for another 0.5 hour at 65° C. At roomtemperature, the cool sulfuric acid solution was slowly added to anice-cold mixture of 325 ml of methylene chloride and 325 ml of water.The phases were separated, the sulfuric acid solution was extractedtwice with 250 ml each time of methylene chloride, the combined organicphases were washed with 200 ml of saturated sodium hydrogencarbonatesolution, 200 ml of water and 200 ml of saturated sodium chloridesolution and dried over magnesium sulfate. After removal of the solvent,the brown liquid was distilled via a 10 cm Vigreux column with columnhead under a full oil pump vacuum. This gave 39.6 g of (1) as a paleyellow liquid which slowly crystallized.

B.p.: 95-98° C. (0.3-0.25 mbar); m.p.: 42-43° C.; ¹H-NMR (300 MHz,CDCl₃): 7.41 (t, 1H), 7.28 (m, 1H), 7.22 (m, 1H), 3.31 (m, 1H),2.59-2.27 (m, 2H), 1.25 (d, J=7.3 Hz, 3H).

2. 7-Bromo-2-methyl-1-indanone (2)

Using a method similar to Example 1, 57.2 g of (2) were obtained assolid from 78.2 g (0.37 mol) of 2-bromopropiophenone (S. Wang et al., J.Org. Chem., 1989, 54, 5364).

M.p.: 55-61° C.; ¹H-NMR (300 MHz, CDCl₃): 7.50 (1H), 7.37 (2H), 3.34 (m,1H), 2.9-2.6 (m, 2H), 1.3 (d, 3H).

3. 2-Methyl-7-trifluoromethanesulfonoxy-1-indanone (3)

16.2 g (0.1 mol) of 7-hydroxy-2-methyl-1-indanone (G. Bringmann et al.,Liebigs Ann. Chem., 1985, 2116) together with 20 ml of dry pyridine in150 ml of dry methylene chloride were placed in the reaction vessel. At−78° C., 20 ml (0.12 mol) of trifluoromethanesulfonic anhydride wereadded and the mixture was slowly warmed to 0° C. on an ice bath. Thereaction mixture was stirred for 16 hours at 20° C., subsequentlydiluted with 750 ml of ether, the precipitated pyridinium salt wasfiltered off, the ether phase was washed twice with 100 ml each time of2N hydrochloric acid, twice with 100 ml each time of water and once with200 ml of saturated sodium chloride solution and dried over magnesiumsulfate. After removal of the solvent, the residue was chromatographedon silica gel using heptane/ethyl acetate (9:1). 27.1 g of (3) wereobtained.

¹H-NMR (300 MHz, CDCl₃): 7.5-7.3 (3H), 3.3 (m, 1H), 2.7-2.4 (m, 2H), 1.3(d, 3H).

4. 7-Iodo-2-methyl-1-indanone (4)

Using a method similar to Example 2, 12.8 g of (4) as solid wereobtained (the cyclization was carried out in polyphosphoric acid insteadof in sulfuric acid) from 30.6 g (0.118 mol) of 2-iodopropiophenone (asdescribed by S. Wang et al., J. Org. Chem., 1989, 54, 5364; but theethyl Grignard was converted into the cuprate by addition of CuI).

¹H-NMR (300 MHz, CDCl₃): 7.50-7.30 (3H), 3.3 (m, 1H), 2.9-2.6 (m, 2H),1.3 (d, 3H).

5. 7-Chloro-2-butyl-1-indanone (5)

Using a method similar to U.S. Pat. No. 5,489,712 or A. Bhattacharya,Synthetic Communications, 1996, 26, 1775, 18.5 g of (5) were obtainedfrom 32.0 g (0.15 mol) of 2-chlorophenyl pentyl ketone (preparationsimilar to that of 2-chloropropiophenone).

¹H-NMR (300 MHz, CDCl₃): 7.5-7.4 (1H), 7.35-7.1 (2H), 3.3-3.1 (1H),2.8-2.7 (1H), 2.7-2.5 (2H), 2.0-1.8 (1H), 1.55-1.2 (5H), 0.9 (t, 3H).

6. 7-Chloro-2-cyclohexyl-1-indanone (6)

Using a method similar to U.S. Pat. No. 5,489,712 or A. Bhattacharya,Synthetic Communications, 1996, 26, 1775, 14 g of7-chloro-2-cyclohexyl-1-indanone (6) were obtained from 20.0 g (0.085mol) of 2-chlorophenyl methylcyclohexyl ketone (preparation similar tothat of 2-chloropropiophenone).

¹H-NMR (300 MHz, CDCl₃): 7.47-7.25 (3H), 3.11 (dd, 1H), 2.92 (dd, 1H),2.65 (m, 1H), 2.10-1.98 (m, 1H), 1.80-1.60 (m, 4H), 1.46-1.0 (m, 6H).

7. 7-Chloro-2-phenyl-1-indanone (7)

Using a method similar to Example 5, 14.5 g of (7) were obtained from23.0 g (0.1 mol) of benzyl 2-chlorophenyl ketone (preparation similar tothat of 7-chloropropiophenone).

8. 7-Bromo-2-isopropyl-1-indanone (8)

Using a method similar to Example 5, 32.8 g of (8) were obtained from48.2 g (0.2 mol) of 2-bromophenyl 2-methylpropyl ketone (preparationsimilar to that of 7-bromopropiophenone).

9. 7-Bromo-2-(2-methylpropyl)-1-indanone (9)

Using a method similar to Example 5, 15.7 g of (9) were obtained from25.5 g (0.1 mol) of 2-bromophenyl 3-methylbutyl ketone (preparationsimilar to that of 7-bromopropiophenone).

10. 7-Bromo-5-fluoro-2-methyl-1-indanone (10)

Using a method similar to Example 2, 7.1 g of (10) were obtained from 15g (0.065 mol) of 2-bromo-4-fluoropropiophenone.

11. 5,7-Dichloro-2-methyl-1-indanone (11)

Using a method similar to Example 1, 26.42 g of (11) were obtained from50 g (0.246 mol) of 2,4-dichloropropiophenone.

12. 6,7-Dichloro-2-methyl-1-indanone (12)

Using a method similar to Example 1, 23.3 g of (12) were obtained from40 g (0.197 mol) of 2,3-dichloropropiophenone.

13. 7-Bromo-2,6-dimethyl-1-indanone (13)

Using a method similar to Example 2, 6.8 g of (13) were obtained from 10g (0.044 mol) of 2-bromo-3-methylpropiophenone.

14. 7-chloro-2-methyl-5-trifluoromethyl-1-indanone (14)

Using a method similar to Example 1, 4.5 g of (14) were obtained from 16g (0.067 mol) of 2-chloro-4-trifluoromethylpropiophenone.

15. 2-Methyl-7-phenyl-1-indanone (15)

-   a) 22.5 g (0.1 mol) of 7-bromo-2-methyl-1-indanone (2), 13.4 g (0.11    mol) of phenylboronic acid and 23.3 g (0.22 mol) of sodium carbonate    were placed in 380 ml of dimethoxyethane and 120 ml of water in the    reaction vessel, the mixture was degassed a number of times and    saturated with argon. 450 mg (2 mmol) of palladium acetate and 1.05    g (4 mmol) of triphenylphosphine (TPP) were added and the reaction    mixture was stirred for 2 hours at 80° C. After addition of 300 ml    of water, the mixture was extracted 3 times with 250 ml each time of    diethyl ether, the ether phase was washed twice with 100 ml each    time of water and dried over magnesium sulfate. Removal of the    solvent gave 21.1 g of (15) as solid.

M.p.: 81.5-83° C.; ¹H-NMR (300 MHz, CDCl₃): 7.6 (t, 1H), 7.5-7.3 (m,6H), 7.25 (1H), 3.4 (m, 1H), 2.8-2.6 (m, 2H), 1.3 (d, 3H).

-   b) 2.5 g (13.8 mmol) of 7-chloro-2-methyl-1-indanone (1), 2.11 g    (17.3 mmol) of phenylboronic acid and 3.66 g (34.6 mmol) of sodium    carbonate were placed in 40 ml of o-xylene/5 ml of water in the    reaction vessel, the mixture was degassed a number of times and    saturated with argon. After addition of 1.55 mg (0.0069 mmol) of    palladium acetate and 7.3 mg (0.027 mmol) of triphenylphosphine, the    reaction mixture was stirred for 8 hours at 100° C. After 2, 4 and 6    hours, the same amount of palladium acetate and triphenylphosphine    were added again each time. After addition of 40 ml of water, the    phases were separated, the aqueous phase was extracted 3 times with    40 ml each time of ether, the combined organic phases were washed    with 40 ml of water and 40 ml of saturated sodium chloride solution    and dried over magnesium sulfate. Removal of the solvent gave 2.9 g    of (15) as solid. The ¹H-NMR indicated a conversion of about 85%.-   c) 0.9 g (5 mmol) of (1), 0.73 g (6 mmol) of phenylboronic acid and    1.32 g (12.5 mmol) of sodium carbonate were placed in 15 ml of    ethylene glycol/3 ml of water in the reaction vessel, the mixture    was degassed a number of times and saturated with argon. After    addition of 33.7 mg (0.15 mmol) of palladium acetate and 0.34 g (0.6    mmol) of (m-NaO₃S-phenyl)₃phosphine (TMSPP), the reaction mixture    was stirred for 5 hours at 125° C. After addition of 20 ml of water,    the aqueous phase was extracted 5 times with 30 ml each time of    ether, the combined ether phases were washed with 40 ml of water and    40 ml of saturated sodium chloride solution and dried over magnesium    sulfate. Removal of the solvent gave 0.76 g of (15) as solid.    16. 2-Methyl-7-(1-naphthyl)-1-indanone (16)-   a) Using a method similar to Example 15 a), 56.3 g (0.25 mol) of    7-bromo-2-methyl-1-indanone (2), 47.3 g (0.275 mol) of    1-naphthylboronic acid and 58 g (0.55 mol) of sodium carbonate were    placed in 950 ml of dimethoxyethane and 300 ml of water in the    reaction vessel, the mixture was degassed a number of times and    saturated with argon. 560 mg (2.5 mmol) of palladium acetate and    1.31 g (5 mmol) of triphenylphosphine (TPP) were added and the    reaction mixture was stirred for 2 hours at 80° C. After addition of    700 ml of water, the mixture was extracted 5 times with 300 ml each    time of diethyl ether, the ether phase was washed twice with 300 ml    each time of water and with 300 ml of saturated sodium chloride    solution and dried over magnesium sulfate. Removal of the solvent    gave 63.3 g of (16) as solid.

M.p: 104-105° C.; ¹H-NMR (300 MHz, CDCl₃): 7.9 (d, 2H), 7.65 (m, 1H),7.6-7.25 (m, 7H), 3.5 (m, 1H), 2.9-2.6 (m, 2H), 1.25 (d, 3H).

-   b) Using a method similar to Example 15 b), 2.5 g (13.8 mmol) of    7-chloro-2-methyl-1-indanone (1), 2.97 g (17.3 mmol) of    naphthylboronic acid and 3.66 g (34.6 mmol) of sodium carbonate were    placed in 40 ml of o-xylene/5 ml of water in the reaction vessel,    the mixture was degassed a number of times and saturated with argon.    After addition of 1.55 mg (0.0069 mmol) of palladium acetate and 7.3    mg (0.027 mmol) of triphenylphosphine, the reaction mixture was    stirred for 8 hours at 100° C. After 2, 4 and 6 hours, the same    amount of palladium acetate and triphenyl phosphine were added again    each time. After addition of 40 ml of water, the phases were    separated, the aqueous phase was extracted 3 times with 40 ml each    time of ether, the combined organic phases were washed with 40 ml of    water and 40 ml of saturated sodium chloride solution and dried over    magnesium sulfate. Removal of the solvent gave 3.26 g of (16) as    solid.-   c) 2.5 g (13.8 mmol) of 7-chloro-2-methyl-1-indanone (1), 2.86 g    (16.6 mmol) of naphthylboronic acid, 0.22 g (0.68 mmol) of    tetrabutylammonium bromide and 3.66 g (34.6 mmol) of sodium    carbonate were placed in 40 ml of o-xylene in the reaction vessel,    the mixture was degassed a number of times and saturated with argon.    After addition of 1.55 mg (0.0069 mmol) of palladium acetate and 7.3    mg (0.027 mmol) of triphenylphosphine, the reaction mixture was    stirred for 9 hours at 125° C. After addition of 40 ml of water, the    phases were separated, the aqueous phase was extracted 3 times with    40 ml each time of ether, the combined organic phases were washed    with 40 ml of water and 40 ml of saturated sodium chloride solution    and dried over magnesium sulfate. Removal of the solvent gave 3.38 g    of (16) as solid.-   d) Using a method similar to Example 15 c), 2.5 g (13.84 mmol) of    (1), 2.86 g (16.6 mmol) of naphthylboronic acid and 3.66 g (34.6    mmol) of sodium carbonate were placed in 41 ml of ethylene    glycol/8.3 ml of water in the reaction vessel, the mixture was    degassed a number of times and saturated with argon. After addition    of 1 mg (0.0046 mmol) of palladium acetate and 10.4 mg (0.0184 mmol)    of TMSPP, the reaction mixture was stirred for 5 hours at 125° C.    The aqueous phase was extracted twice with 50 ml each time of ether,    the combined ether phases were washed with 40 ml of water and 40 ml    of saturated sodium chloride solution and dried over magnesium    sulfate. Removal of the solvent gave 3.08 g of (16) as solid.    17. 7-(3,5-Dimethylphenyl)-2-methyl-1-indanone (17)

Using a method similar to Example 16 b), 16.25 g (0.09 mol) of (1),14.85 g (0.1 mol) of 3,5-dimethylphenylboronic acid, 21.2 g (0.2 mol) ofsodium carbonate were placed in 240 ml of o-xylene/80 ml of water in thereaction vessel, the mixture was degassed a number of times andsaturated with argon. After addition of 101 mg (0.45 mmol) of palladiumacetate and 472 mg (1.8 mmol) of TPP, the reaction mixture was stirredfor 8 hours at 100° C. After 2, 4 and 6 hours, the same amounts ofpalladium acetate and triphenylphosphine were added again each time.After addition of 150 ml of water, the phases were separated, theaqueous phase was extracted 3 times with 200 ml each time of ether, thecombined organic phases were washed with 200 ml of water and 200 ml ofsaturated sodium chloride solution and dried over magnesium sulfate.Removal of the solvent gave 20.3 g of (17) as an oil.

¹H-NMR (300 MHz, CDCl₃): 7.55 (t, 1H), 7.4 (m, 1H), 7.23 (1H), 7.05 (m,2H), 7.02 (1H), 3.34 (m, 1H), 2.78-2.64 (m, 2H), 2.35 (s, 6H), 1.27 (d,3H).

18. 7-(3,5-Bis(trifluoromethyl)phenyl)-2-methyl-1-indanone (18)

Using a method similar to Example 15 a), 6.75 g (0.03 mol) of (2), 8.5 g(0.033 mol) of 3,5-bis(trifluoromethyl)phenylboronic acid and 7.0 g(0.066 mol) of sodium carbonate were placed in 120 ml of dimethoxyethaneand 36 ml of water in the reaction vessel, the mixture was degassed anumber of times and saturated with argon. 120 mg (0.5 mmol) of palladiumacetate and 282 mg (1.1 mmol) of TPP were added and the reaction mixturewas stirred for 2 hours at 80° C. After addition of 150 ml of water, themixture was extracted 3 times with 150 ml each time of diethyl ether,the combined ether phases were washed 3 times with 150 ml each time ofwater and dried over magnesium sulfate. Removal of the solvent gave 9.93g of (18) as an oil.

¹H-NMR (300 MHz, CDCl₃): 7.9 (s, 2H), 7.66 (t, 1H), 7.53 (dd, 1H),7.3-7.24 (2H), 3.46 (m, 1H), 2.83-2.70 (m, 2H), 1.29 (d, 3H).

19. 2-Methyl-7-(2-naphthyl)-1-indanone (19)

Using a method similar to Example 16 d), 2.16 g (0.012 mol) of (1), 2.27g (0.0132 mol) of 2-naphthylboronic acid, 2.8 g (0.0264 mol) of sodiumcarbonate were placed in 40 ml of ethylene glycol/8 ml of water in thereaction vessel, the mixture was degassed a number of times andsaturated with argon. After addition of 13.5 mg (0.06 mmol) of palladiumacetate and 0.102 g (0.18 mmol) of TMSPP, the reaction mixture wasstirred for 2 hours at 125° C. After addition of 40 ml of water, theaqueous phase was extracted 4 times with 50 ml each time of ether, thecombined ether phases were washed with 50 ml of water and 50 ml ofsaturated sodium chloride solution and dried over magnesium sulfate.Removal of the solvent gave 3.0 g of (19) as an oil which tends tocrystallize.

¹H-NMR (300 MHz, CDCl₃): 7.92 (m, 4H), 7.62 (2H), 7.56-7.49 (m, 2H),7.46 (dd, 1H), 7.39 (d, 1H), 3.45 (m, 1H), 2.84-2.68 (m, 2H), 2.35 (s,6H), 1.33 (d, 3H).

20. 7-(4-Methoxyphenyl)-2-methyl-1-indanone (20)

Using a method similar to Example 16 d), 3.84 g (0.021 mol) of (1), 3.58g (0.024 mol) of 4-methoxyphenylboronic acid, 4.98 g (0.047 mol) ofsodium carbonate were placed in 60 ml of ethylene glycol/10 ml of waterin the reaction vessel, the mixture was degassed a number of times andsaturated with argon. After addition of 23.9 mg (0.106 mmol) ofpalladium acetate and 0.12 g (0.21 mmol) of TMSPP, the reaction mixturewas stirred for 2 hours at 125° C. After addition of 60 ml of water, theaqueous phase was extracted 4 times with 60 ml each time of ether, thecombined ether phases were washed with 60 ml of water and 60 ml ofsaturated sodium chloride solution and dried over magnesium sulfate.Removal of the solvent gave 3.75 g of (20) as an oil.

¹H-NMR (300 MHz, CDCl₃): 7.55 (t, 1H), 7.40 (m, 2H), 7.36 (m, 1H), 7.24(m, 1H), 6.94 (m, 2H), 3.84 (s, 3H), 3.39 (m, 1H), 2.77-2.63 (m, 2H),1.28 (d, 3H).

21. 2-Methyl-7-(4-methylphenyl)-1-indanone (21)

Using a method similar to Example 16 d), 3.61 g (0.020 mol) of (1), 3.0g (0.022 mol) of 4-methylphenylboronic acid, 4.66 g (0.044 mol) ofsodium carbonate were placed in 60 ml of ethylene glycol/12 ml of waterin the reaction vessel, the mixture was degassed a number of times andsaturated with argon. After addition of 22.4 mg (0.1 mmol) of palladiumacetate and 0.114 g (0.2 mmol) of TMSPP, the reaction mixture wasstirred for 2 hours at 125° C. After addition of 60 ml of water, theaqueous phase was extracted 4 times with 50 ml each time of ether, thecombined ether phases were washed with 50 ml of water and 50 ml ofsaturated sodium chloride solution and dried over magnesium sulfate.Removal of the solvent gave 4.5 g of (21) as solid.

¹H-NMR (300 MHz, CDCl₃): 7.56 (t, 1H), 7.42-7.14 (m, 6H), 3.40 (m, 1H),2.78-2.64 (m, 2H), 2.40 (s, 3H), 1.28 (d, 3H).

22. 2-Methyl-7-(2-thienyl)-1-indanone (22)

Using a method similar to Example 15 a), 11.25 g (0.05 mol) of (2), 13.4g (0.055 mol) of thiophenylboronic acid and 11.7 g (0.11 mol) of sodiumcarbonate were placed in 190 ml of dimethoxyethane and 60 ml of water inthe reaction vessel, the mixture was degassed a number of times andsaturated with argon. 225 mg (1 mmol) of palladium acetate and 0.609 g(2 mmol) of tris(o-tolylphenyl)phosphine were added and the reactionmixture was stirred for 2 hours at 80° C. After addition of 150 ml ofwater, the mixture was extracted 4 times with 100 ml each time ofdiethyl ether, the ether phase was washed twice with 50 ml each time ofwater and dried over magnesium sulfate. Removal of the solvent gave 8.6g of (22) as an oil.

¹H-NMR (300 MHz, CDCl₃): 7.6 (t, 1H), 7.5-7.3 (m, 6H), 7.25 (1H), 3.4(m, 1H), 2.8-2.6 (m, 2H), 1.3 (d, 3H).

23. 2-Methyl-7-(2-furanyl)-1-indanone (23)

Using a method similar to Example 22, 33.7 g (0.15 mol) of (2), 18.5 g(0.165 mol) of furanylboronic acid and 34.9 g (0.33 mol) of sodiumcarbonate were placed in 570 ml of dimethoxyethane and 180 ml of waterin the reaction vessel, the mixture was degassed a number of times andsaturated with argon. 675 mg (3 mmol) of palladium acetate and 1.83 g (6mmol) of tris(o-tolylphenyl)phosphine were added and the reactionmixture was stirred for 2 hours at 80° C. After addition of 450 ml ofwater, the mixture was extracted 4 times with 300 ml each time ofdiethyl ether, the ether phase was washed twice with 200 ml each time ofwater and dried over magnesium sulfate. Removal of the solvent gave27.06 g of (23) as an oil.

¹H-NMR (300 MHz, CDCl₃): 7.86 (m, 2H), 7.57 (t, 1H), 7.51 (m, 1H),7.4-7.2 (m, 2H), 3.37 (m, 1H), 2.78-2.66 (m, 2H), 1.32 (d, 3H).

24. 2-Methyl-7-(2-pyridyl)-1-indanone (24)

16.9 g (75 mmol) of (2) and 20 g (90 mmol) of 2-trimethylstannylpyridinewere placed in 165 ml of tetrahydrofuran in the reaction vessel, themixture was degassed a number of times and saturated with argon. 350 mg(0.37 mmol) oftrans-di(μ-acetato)bis-[o-(di-o-tolylphosphino)benzyl]dipalladium (II)were added and the reaction mixture was refluxed for 24 hours. Afteraddition of 200 ml of water, the mixture was extracted 4 times with 150ml each time of diethyl ether, the ether phase was washed with 100 ml ofwater and 100 ml of saturated sodium chloride solution and dried overmagnesium sulfate. Removal of the solvent and drying for 24 hours at 0.1mbar at 60° C. (removal of the trimethylstannyl bromide) gave 15.07 g of(24) as an oil.

¹H-NMR (300 MHz, CDCl₃): 8.66 (m, 1H), 7.66-7.20 (5H), 3.40 (m, 1H),2.78-2.64 (m, 2H), 1.25 (d, 3H).

25. 2-Methyl-7-(2-methylphenyl)-1-indanone (25)

Using a method similar to Example 16 d), 2.0 g (0.011 mol) of (1), 1.82g (0.013 mol) of 2-methylphenylboronic acid and 2.6 g (24.6 mmol) ofsodium carbonate were placed in 55 ml of ethylene glycol/5 ml of waterin the reaction vessel, the mixture was degassed a number of times andsaturated with argon. After addition of 18 mg (0.09 mmol) of palladiumacetate and 0.15 g (0.27 mmol) of TMSPP, the reaction mixture wasstirred for 2 hours at 125° C. After addition of 60 ml of water, theaqueous phase was extracted 4 times with 60 ml each time of ether, thecombined ether phases were washed with 60 ml of water and 60 ml ofsaturated sodium chloride solution and dried over magnesium sulfate.Removal of the solvent gave 2.1 g of2-methyl-7-(2-methylphenyl)-1-indanone as solid.

¹H-NMR (300 MHz, CDCl₃): 7.66-7.10 (m, 7H), 3.48 (m, 1H), 2.86-2.64 (m,2H), 2.13/2.11 (s, 3H, stereoisomers), 1.33/1.29 (d, 3H, stereoisomers).

26. 2-Methyl-7-(4-dimethylaminophenyl)-1-indanone (26)

Using a method similar to Example 22, 8.0 g (0.032 mol) of (2), 5.85 g(0.038 mol) of 4-dimethylaminophenylboronic acid and 7.4 g (0.07 mol) ofsodium carbonate were placed in 122 ml of dimethoxyethane and 37 ml ofwater in the reaction vessel, the mixture was degassed a number of timesand saturated with argon. 142 mg (0.6 mmol) of palladium acetate and 385mg (1.3 mmol) of tris(o-tolylphenyl)phosphine were added and thereaction mixture was stirred for 4 hours at 80° C. After addition of 150ml of water, the mixture was extracted 4 times with 100 ml each time ofdiethyl ether, the ether phase was washed twice with 50 ml each time ofwater and dried over magnesium sulfate. Removal of the solvent andcolumn filtration through neutral aluminum oxide (dichloromethane) gave6.5 g of 2-methyl-7-(4-dimethylaminophenyl)-1-indanone as an oil.

¹H-NMR (300 MHz, CDCl₃): 7.58-7.24 (m, 5H), 6.78 (d, 2H), 3.38 (m, 1H),3.01 (s, 6H), 2.78-2.65 (m, 2H), 1.28 (d, 2H).

27. 2-Methyl-7-(2,3-dimethylphenyl)-1-indanone (27)

Using a method similar to Example 16 d), 2.0 g (0.011 mol) of (1), 1.95g (0.013 mol) of 2,3-dimethylphenylboronic acid and 2.6 g (24.6 mmol) ofsodium carbonate were placed in 55 ml of ethylene glycol/5 ml of waterin the reaction vessel, the mixture was degassed a number of times andsaturated with argon. After addition of 18 mg (0.09 mmol) of palladiumacetate and 0.15 g (0.27 mmol) of TMSPP, the reaction mixture wasstirred for 2 hours at 125° C. After addition of 60 ml of water, theaqueous phase was extracted 4 times with 60 ml each time of ether, thecombined ether phases were washed with 60 ml of water and 60 ml ofsaturated sodium chloride solution and dried over magnesium sulfate.Removal of the solvent gave 2.9 g of2-methyl-7-(2,3-dimethylphenyl)-1-indanone as solid.

¹H-NMR (300 MHz, CDCl₃): 7.61-6.92 (m, 6H), 3.40 (m, 1H), 2.80-2.60 (m,2H), 2.34/2.32 (s, 3H, stereoisomers), 1.97/1.93 (s, 3H, stereoisomers),1.26/1.23 (d, 3H, stereoisomers).

28. 2-Methyl-7-(4-vinylphenyl)-1-indanone (28)

Using a method similar to Example 16 d), 2.0 g (0.011 mol) of (1), 1.92g (0.013 mol) of 4-styreneboronic acid and 2.6 g (24.6 mmol) of sodiumcarbonate were placed in 55 ml of ethylene glycol/5 ml of water in thereaction vessel, the mixture was degassed a number of times andsaturated with argon. After addition of 18 mg (0.09 mmol) of palladiumacetate and 0.15 g (0.27 mmol) of TMSPP, the reaction mixture wasstirred for 2 hours at 125° C. After addition of 60 ml of water, theaqueous phase was extracted 4 times with 60 ml each time of ether, thecombined ether phases were washed with 60 ml of water and 60 ml ofsaturated sodium chloride solution and dried over magnesium sulfate.Removal of the solvent gave 2.2 g of2-methyl-7-(4-vinylphenyl)-1-indanone.

¹H-NMR (300 MHz, CDCl₃): 7.60-7.26 (m, 7H), 6.78 (dd, 1H), 5.81 (d, 1H),5.28 (d, 1H), 3.42 (m, 1H), 2.80-2.67 (m, 2H), 1.31 (d, 3H).

29. 2-Methyl-7-(4-trifluoromethylphenyl)-1-indanone (29)

Using a method similar to Example 16 d), 6.28 g (0.035 mol) of (1), 7.6g (0.040 mol) of 4-trifluoromethylphenylboronic acid and 8.16 g (77.3mmol) of sodium carbonate were placed in 160 ml of ethylene glycol/17 mlof water in the reaction vessel, the mixture was degassed a number oftimes and saturated with argon. After addition of 57 mg (0.283 mmol) ofpalladium acetate and 0.47 g (0.848 mmol) of TMSPP, the reaction mixturewas stirred for 2 hours at 125° C. After addition of 170 ml of water,the aqueous phase was extracted 4 times with 100 ml each time of ether,the combined ether phases were washed with 60 ml of water and 60 ml ofsaturated sodium chloride solution and dried over magnesium sulfate.Removal of the solvent gave 9.54 g of2-methyl-7-(4-trifluoromethylphenyl)-1-indanone.

¹H-NMR (300 MHz, CDCl₃): 7.80-7.26 (m, 7H), 3.42 (m, 1H), 2.80-2.67 (m,2H), 1.31 (d, 3H).

30. 2-Methyl-7-(4-biphenyl)-1-indanone (30)

Using a method similar to Example 15 a), 6.75 g (0.03 mol) of (2), 6.53g (0.033 mol) of 4-biphenylphenylboronic acid and 7.0 g (0.066 mol) ofsodium carbonate were placed in 120 ml of dimethoxyethane and 36 ml ofwater in the reaction vessel, the mixture was degassed a number of timesand saturated with argon. 120 mg (0.5 mmol) of palladium acetate and 282mg (1.1 mmol) of TPP were added and the reaction mixture was stirred for2 hours at 80° C. After addition of 150 ml of water, the mixture wasextracted 3 times with 150 ml each time of diethyl ether, the combinedether phases were washed 3 times with 150 ml each time of water anddried over magnesium sulfate. Removal of the solvent gave 7.78 g of2-methyl-7-(4-biphenyl)-1-indanone.

¹H-NMR (300 MHz, CDCl₃): 7.67-7.14 (12H), 3.49-3.37 (m, 1H), 2.80-2.67(m, 2H), 1.30 (d, 3H).

31. 2-Methyl-7-(4-tert-butylphenyl)-1-indanone (31)

Using a method similar to Example 16 d), 2.0 g (0.011 mol) of (1), 2.31g (0.013 mol) of 4-tert-butylphenylboronic acid and 2.6 g (24.6 mmol) ofsodium carbonate were placed in 55 ml of ethylene glycol/5 ml of waterin the reaction vessel, the mixture was degassed a number of times andsaturated with argon. After addition of 18 mg (0.09 mmol) of palladiumacetate and 0.15 g (0.27 mmol) of TMSPP, the reaction mixture wasstirred for 2 hours at 125° C. After addition of 60 ml of water, theaqueous phase was extracted 4 times with 60 ml each time of ether, thecombined ether phases were washed with 60 ml of water and 60 ml ofsaturated sodium chloride solution and dried over magnesium sulfate.Removal of the solvent gave 2.8 g of2-methyl-7-(4-tert-butylphenyl)-1-indanone.

¹H-NMR (300 MHz, CDCl₃): 7.60-7.26 (m, 7H), 3.42 (m, 1H), 2.80-2.67 (m,2H), 1.31 (9H), 1.28 (d, 3H).

32. 2-Methyl-7-(3,5-difluorophenyl)-1-indanone (32)

2.25 g (0.01 mol) of 7-bromo-2-methyl-1-indanone (2), 1.74 g (0.011 mol)of 3,5-difluorophenylboronic acid and 2.33 g (0.022 mol) of sodiumcarbonate were placed in 38 ml of dimethoxyethane and 12 ml of water inthe reaction vessel, the mixture was degassed a number of times andsaturated with argon. 45 mg (0.2 mmol) of palladium acetate and 0.1 g(0.4 mmol) of triphenylphosphine (TPP) were added and the reactionmixture was stirred for 2 hours at 80° C. After addition of 50 ml ofwater, the mixture was extracted 3 times with 30 ml each time of diethylether, the ether phase was washed twice with water and dried overmagnesium sulfate. Removal of the solvent gave 2.4 g of2-methyl-7-(3,5-difluorophenyl)-1-indanone as solid.

¹H-NMR (300 MHz, CDCl₃): 7.62-7.31 (m, 6H), 3.43 (m, 1H), 2.8-2.6 (m,2H), 1.29 (d, 3H).

33. 2-Butyl-7-phenyl-1-indanone (33)

Using a method similar to Example 16 d), 10.02 g (0.045 mol) of2-butyl-7-chloro-1-indanone, 6.58 g (0.054 mol) of phenylboronic acidand 11.9 g (0.122 mol) of sodium carbonate were placed in 135 ml ofethylene glycol/27 ml of water in the reaction vessel, the mixture wasdegassed a number of times and saturated with argon. After addition of 5mg (0.022 mmol) of palladium acetate and 0.051 g (0.09 mmol) of TMSPP,the reaction mixture was stirred for 5 hours at 125° C. After additionof 120 ml of water, the aqueous phase was extracted 4 times with 100 mleach time of ether, the combined ether phases were washed with 50 ml ofwater and 50 ml of saturated sodium chloride solution and dried overmagnesium sulfate. Removal of the solvent gave 12.0 g of (33) as an oil.

¹H-NMR (300 MHz, CDCl₃): 7.58 (t, 1H), 7.47-7.35 (6H), 7.28-7.23 (1H),3.34 (dd, 1H), 2.83 (dd, 1H), 2.65 (m, 1H), 1.94 (m, 1H), 1.41 (m, 5H),0.91 (t, 3H).

34. 2-Butyl-7-(1-naphthyl)-1-indanone (34)

Using a method similar to Example 16 d), 10.02 g (0.045 mol) of2-butyl-7-chloro-1-indanone, 10.06 g (0.0585 mol) of 1-naphthylboronicacid and 11.9 g (0.122 mol) of sodium carbonate were placed in 135 ml ofethylene glycol/27 ml of water in the reaction vessel, the mixture wasdegassed a number of times and saturated with argon. After addition of 5mg (0.022 mmol) of palladium acetate and 0.051 g (0.09 mmol) of TMSPP,the reaction mixture was stirred for 5 hours at 125° C. After additionof 120 ml of water, the aqueous phase was extracted 4 times with 100 mleach time of ether, the combined ether phases were washed with 50 ml ofwater and 50 ml of saturated sodium chloride solution and dried overmagnesium sulfate. Removal of the solvent gave 12.2 g of (34) as an oil.

¹H-NMR (300 MHz, CDCl₃): 7.93 (d, 2H), 7.71-7.20 (8H), 3.39 (m, 1H),2.92 (m, 1H), 2.64 (m, 1H), 1.88 (m, 1H), 1.41 (m, 5H), 0.93 (t, 3H).

35. 2-Cyclohexyl-7-phenyl-1-indanone (35)

Using a method similar to Example 16 d), 2.73 g (0.011 mol) of2-cyclohexyl-7-chloro-1-indanone, 1.59 g (0.013 mol) of phenylboronicacid and 2.6 g (24.6 mmol) of sodium carbonate were placed in 55 ml ofethylene glycol/5 ml of water in the reaction vessel, the mixture wasdegassed a number of times and saturated with argon. After addition of18 mg (0.09 mmol) of palladium acetate and 0.15 g (0.27 mmol) of TMSPP,the reaction mixture was stirred for 2 hours at 125° C. After additionof 60 ml of water, the aqueous phase was extracted 4 times with 60 mleach time of ether, the combined ether phases were washed with 60 ml ofwater and 60 ml of saturated sodium chloride solution and dried overmagnesium sulfate. Removal of the solvent gave 2.9 g of2-cyclohexyl-7-phenyl-1-indanone.

¹H-NMR (300 MHz, CDCl₃): 7.60-7.16 (m, 8H), 3.11 (dd, 1H), 2.92 (dd,1H), 2.65 (m, 1H), 2.10-1.98 (m, 1H), 1.80-1.60 (m, 4H), 1.46-1.0 (m,6H).

36. 2-Cyclohexyl-7-(1-naphthyl)-1-indanone (36)

Using a method similar to Example 16 d), 2.73 g (0.011 mol) of2-cyclohexyl-7-chloro-1-indanone, 2.24 g (0.013 mol) of naphthylboronicacid and 2.6 g (24.6 mmol) of sodium carbonate were placed in 55 ml ofethylene glycol/5 ml of water in the reaction vessel, the mixture wasdegassed a number of times and saturated with argon. After addition of18 mg (0.09 mmol) of palladium acetate and 0.15 g (0.27 mmol) of TMSPP,the reaction mixture was stirred for 2 hours at 125° C. After additionof 60 ml of water, the aqueous phase was extracted 4 times with 60 mleach time of ether, the combined ether phases were washed with 60 ml ofwater and 60 ml of saturated sodium chloride solution and dried overmagnesium sulfate. Removal of the solvent gave 3.0 g of2-cyclohexyl-7-(1-naphthyl)-1-indanone.

¹H-NMR (300 MHz, CDCl₃): 7.92-7.20 (10H), 3.11 (dd, 1H), 2.92 (dd, 1H),2.65 (m, 1H), 2.10-1.98 (m, 1H), 1.80-1.60 (m, 4H), 1.46-1.0 (m, 6H).

37. 2-Methyl-4-(1-naphthyl)indene (37)

1.3 g (33 mmol) of sodium borohydride were added at 0° C. to a solutionof 12 g (44 mmol) of (16) in 100 ml of THF/methanol 2:1 and the mixturewas stirred for 18 hours at room temperature. The reaction mixture waspoured onto 100 g of ice, concentrated hydrochloric acid was added untilthe pH was 1 and the mixture was extracted a number of times withdiethyl ether. The combined organic phases were washed with saturatedaqueous sodium hydrogen carbonate solution, water and saturated aqueoussodium chloride solution and dried over magnesium sulfate. The crudeproduct was taken up in 200 ml of toluene, admixed with 0.5 g ofp-toluenesulfonic acid and refluxed for 2 hours on a water separator.The reaction mixture was washed 3 times with 509 ml each time ofsaturated sodium hydrogen carbonate solution and the solvent was removedunder reduced pressure. The solid residue was washed with a littlepentane and dried under reduced pressure. This gave 10.3 g of (37) inthe form of colorless crystals.

m.p. 143° C.; ¹H-NMR (300 MHz, CDCl₃): 7.92-7.18 (10H), 6.11 (m, 1H),3.42 (s, 2H), 2.07 (3H).

Using a method similar to Example 37, the following indenes wereprepared:

38. 2-Methyl-4(or 7)-phenylindene (38)

39. 2-Methyl-4(or 7)-(4-methoxyphenyl)indene (39)

40. 2-Methyl-4(or 7)-(4-methylphenyl)indene (40)

41. 2-Methyl-4(or 7)-(2-methylphenyl)indene (41)

42. 2-Methyl-4(or 7)-(2,3-dimethylphenyl)indene (42)

43. 2-Methyl-4(or 7)-(3,5-bis(trifluoromethyl)phenyl)indene (43)

44. 2-Methyl-4(or 7)-(3,5-dimethylphenyl)indene (44)

45. 2-Methyl-4(or 7)-(3,5-difluorophenyl)indene (45)

46. 2-Methyl-4(or 7)-(2-naphthyl)indene (46)

47. 2-Methyl-4(or 7)-(4-N,N-dimethylaminophenyl)indene (47)

48. 2-Methyl-4(or 7)-(4-trifluoromethylphenyl)indene (48)

49. 2-Methyl-4(or 7)-(4-tert-butylphenyl)indene (49)

50. 2-Methyl-4(or 7)-(4-biphenyl)indene (50)

51. 2-Methyl-4(or 7)-(2-furanyl)indene (51)

52. 2-Methyl-4(or 7)-(2-thienyl)indene (52)

53. 2-Methyl-4(or 7)-(2-pyridyl)indene (53)

54. 2-Butyl-4(or 7)-phenylindene (54)

55. 2-Butyl-4(or 7)-(1-naphthyl)indene (55)

56. 2-Cyclohexyl-4(or 7)-phenylindene (56)

57. 2-Cyclohexyl-4(or 7)-(1-naphthyl)indene (57)

58. Dimethylsilanediylbis(2-methyl-4-(1-naphthyl)indenyl)zirconiumdichloride (58)

14.4 ml (50 mmol) of a 20% strength solution of butyllithium in toluenewere added at room temperature to a solution of 10 g (38 mmol) of (37)in 100 ml of toluene and 5 ml of THF and the mixture was heated at 80°C. for 2 hours. The suspension was subsequently cooled to 0° C. andadmixed with 2.5 g (19 mmol) of dimethyldichlorosilane. The reactionmixture was heated at 80° C. for another 1 hour and subsequently washedwith 50 ml of water. The solvent was removed under reduced pressure andthe residue was recrystallized from heptane at −20° C. 8.2 g of ligandwere obtained as colorless crystals. 8.0 g (14 mmol) of the ligand weredissolved in 70 ml of diethyl ether, admixed at room temperature with10.5 ml of a 20% strenght solution of butyllithium in toluene andsubsequently refluxed for 3 hours. The solvent was removed under reducedpressure and the residue together with 50 ml of hexane was filtered on aG3 Schlenk frit, washed with 50 ml of hexane and dried (0.1 mbar, 20°C.). The dilithium salt was added at −78° C. to a suspension of 3.2 g(14 mmol) of zirconium tetrachloride in 80 ml of methylene chloride and,while stirring, warmed to room temperature over a period of 18 hours.The mixture was filtered on a G3 frit and the residue was extracted witha total of 400 ml of methylene chloride added a little at a time. Thecombined filtrates were very largely freed of solvent under reducedpressure. The crystals which precipitated from methylene chloride wereisolated. This gave 1.5 g of (58) having a racemate:meso ratio of 1:1.Recrystallization from methylene chloride gave the racemic complex inthe form of yellow crystals.

¹H-NMR (300 MHz, CDCl₃): 7.94-7.10 (m, 20H), 6.49 (s, 2H), 2.22 (s, 6H),1.36 (6H).

59.Dimethylsilanediylbis(2-methyl-4-(3,5-bistrifluoromethyl)phenyl)indenyl)zirconiumdichloride (59)

Using a method similar to Example 58,2-methyl-7-(3,5-bis-(trifluoromethyl)phenyl)indene was converted intothe corresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 8.11-6.91 (m, 12H), 6.84/6.72 (s, 2H),2.50/2.27 (s, 6H), 1.52-1.30 (m, 6H).

60.Dimethylsilanediylbis(2-methyl-4-(3,5-dimethylphenyl)indenyl)zirconiumdichloride (60)

Using a method similar to Example 58,2-methyl-7-(3,5-dimethylphenyl)indene was converted into thecorresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 7.67-6.84 (m, 14H), 2.47-2.27 (m, 18H),1.47-1.25 (m, 6H).

61. Dimethylsilanediylbis(2-methyl-4-(4-methoxyphenyl)indenyl)zirconiumdichloride (61)

Using a method similar to Example 58, 2-methyl-7-(4-methoxyphenyl)indenewas converted into the corresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 7.54-6.8 (m, 16H), 3.81 (s, 6H), 2.45-2.28 (m,6H), 1.45-1.28 (m, 6H).

62. Dimethylsilanediylbis(2-methyl-4-(4-methylphenyl)indenyl)zirconiumdichloride (62)

Using a method similar to Example 58, 2-methyl-7-(4-methylphenyl)indenewas converted into the corresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 7.54-6.8 (m, 16H), 2.48-2.22 (m, 12H),1.50-1.25 (m, 6H).

63. Dimethylsilanediylbis(2-methyl-4-(2-methylphenyl)indenyl)zirconiumdichloride (63)

Using a method similar to Example 58, 2-methyl-7-(2-methylphenyl)indenewas converted into the corresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 7.58-6.90 (m, 16H), 2.49-2.20 (m, 12H),1.51-1.27 (m, 6H).

64. Dimethylsilanediylbis(2-methyl-4-(2-naphthyl)indenyl)zirconiumdichloride (64)

Using a method similar to Example 58, 2-methyl-7-(2-naphthyl)indene wasconverted into the corresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 8.2-7.18 (m, 20H), 6.03 (s, 2H), 2.30 (s, 6H),1.36 (6H).

65.Dimethylsilanediylbis(2-methyl-4-(4-tert-butylphenyl)indenyl)zirconiumdichloride (65)

Using a method similar to Example 58,2-methyl-7-(4-tert-butylphenyl)indene was converted into thecorresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 7.54-6.8 (m, 16H), 2.48-2.22 (m, 6H), 1.50-1.25(m, 6H), 1.32 (s, 18H).

66.Dimethylsilanediylbis(2-methyl-4-(2,3-dimethylphenyl)indenyl)zirconiumdichloride (66)

Using a method similar to Example 58,2-methyl-7-(2,3-dimethylphenyl)indene was converted into thecorresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 7.54-6.8 (m, 16H), 2.48-2.22 (m, 18H),1.50-1.25 (m, 6H).

67.Dimethylsilanediylbis(2-methyl-4-(4-trifluoromethylphenyl)indenyl)zirconiumdichloride (67)

Using a method similar to Example 58,2-methyl-7-(4-trifluoromethylphenyl)indene was converted into thecorresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 7.75-6.88 (m, 16H), 2.50-2.27 (m, 6H),1.49-1.22 (m, 6H).

68.Dimethylsilanediylbis(2-methyl-4-(3,5-difluorophenyl)indenyl)zirconiumdichloride (68)

Using a method similar to Example 58,2-methyl-7-(3,5-difluorophenyl)indene was converted into thecorresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 7.54-6.8 (m, 16H), 2.48-2.22 (m, 6H), 1.50-1.25(m, 6H).

69. Dimethylsilanediylbis(2-methyl-4-(4-biphenyl)indenyl)zirconiumdichloride (69)

Using a method similar to Example 58, 2-methyl-7-(4-biphenyl)indene wasconverted into the corresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 7.76-7.03 (m, 26H), 2.28 (s, 6H), 1.37 (m, 6H).

70. Dimethylsilanediylbis(2-butyl-4-phenyl)indenyl)zirconium dichloride(70)

Using a method similar to Example 58, 2-butyl-4-phenylindene wasconverted into the corresponding dimethylsilyl-bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃): 7.70-6.80 (m, 18H), 2.75 (m, 4H), 1.6-1.3 (m,8H), 1.49, 1.32, 1.22 (s, rac, meso, 6H), 0.91-0.82 (m, 6H).

71.Dimethylsilanediylbis(2-methyl-4-(4-dimethylaminophenyl)indenyl)zirconiumdichloride

Using a method similar to Example 58,2-methyl-4-(4-dimethylaminophenyl)indene was converted into thecorresponding bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃):7.62-7.00 (m, 10H), 6.88-6.76 (m, 6H), 2.95 (s,12H), 2.42 (s, 6H), 1.18 (s, 6H).

72. Dimethylsilanediylbis(2-cyclohexyl-4-phenyl)indenyl)zirconiumdichloride

Using a method similar to Example 58, 2-cyclohexyl-4-phenylindene wasconverted into the corresponding bridged zirconocene.

¹H-NMR (300 MHz, CDCl₃):7.65-7.06 (m, 16H), 6.92 (s, 2H), 2.88-2.75 (m,2H), 2.00-0.95 (m, 20H), 138 (s, 6H).

1. An indanone on the formula (Ia)

wherein X is chlorine, bromine, iodine, triflate or mesylate, R¹ isethyl, isopropyl, n-butyl or sec-butyl Y¹ and Y3 hydrogen and Y² ishydrogen, chlorine, bromine, iodine, triflate or mesylate.
 2. Anindanone of the formula (IIa)

wherein R¹ is a linear, branched or cyclic C₁-C₈-alkyl group, R³ is4-(C₄-C₈-alkyl)phenyl, where the 4-(C₄-C₈-alkyl)group is a branchedC₄-C₈-alkyl group Y⁴ and Y⁶ are each hydrogen and Y⁵ is a hydrogen atomor R₃.
 3. The indanone of claim 2, wherein R¹ is methyl, ethyl,isopropyl, n-butyl or sec.-butyl, R³ is 4-(tert-butyl)phenyl, Y⁴, Y⁵,and Y⁶ are each hydrogen.